Showing papers on "Corrosion published in 2015"

Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode

Abstract: This comparative work studies the self-enforcing heterogeneity of lithium deposition and dissolution as the cause for dendrite formation on the lithium metal anode in various liquid organic solvent based electrolytes. In addition, the ongoing lithium corrosion, its rate and thus the passivating quality of the SEI are investigated in self-discharge measurements. The behavior of the lithium anode is characterized in two carbonate-based standard electrolytes, 1 M LiPF6 in EC/DEC (3 : 7) and 1 M LiPF6 in EC/DMC (1 : 1), and in two alternative electrolytes 1 M LiPF6 in TEGDME and 1 M LiTFSI in DMSO, which have been proposed in the literature as promising electrolytes for lithium metal batteries, more specifically for lithium/air batteries. As a result, electrolyte decomposition, SEI and dendrite formation at the lithium electrode as well as their mutual influences are understood in the development of overpotentials, surface resistances and lithium electrode surface morphologies in subsequent lithium deposition and dissolution processes. A general model of different stages of these processes could be elaborated.

Review of Recent Developments in the Field of Magnesium Corrosion

Abstract: This paper provides a review of recent developments in the field of Mg corrosion and puts those into context. This includes considerations of corrosion manifestations, material influences, surface treatment, anodization, coatings, inhibition, biodegradable medical applications, stress corrosion cracking, flammability, corrosion mechanisms for HP Mg, critical evaluation of corrosion mechanisms, and concluding remarks. There has been much research recently, and much research continues in this area. This is expected to produce significantly better, more-corrosion-resistant Mg alloys.

A high-specific-strength and corrosion-resistant magnesium alloy

Abstract: Ultra-lightweight alloys with high strength, ductility and corrosion resistance are desirable for applications in the automotive, aerospace, defence, biomedical, sporting and electronic goods sectors. Ductility and corrosion resistance are generally inversely correlated with strength, making it difficult to optimize all three simultaneously. Here we design an ultralow density (1.4 g cm−3) Mg–Li-based alloy that is strong, ductile, and more corrosion resistant than Mg-based alloys reported so far. The alloy is Li-rich and a solute nanostructure within a body-centred cubic matrix is achieved by a series of extrusion, heat-treatment and rolling processes. Corrosion resistance from the environment is believed to occur by a uniform lithium carbonate film in which surface coverage is much greater than in traditional hexagonal close-packed Mg-based alloys, explaining the superior corrosion resistance of the alloy. A magnesium-based alloy with large lithium content demonstrates high specific strength in combination with corrosion resistance, associated with the formation of a lithium carbonate surface film that protects the alloy from its environment.

Some Quinoxalin-6-yl Derivatives as Corrosion Inhibitors for Mild Steel in Hydrochloric Acid: Experimental and Theoretical Studies

Abstract: The inhibition of mild steel corrosion in 1 M HCl by some quinoxalin-6-yl derivatives namely 1-[3-phenyl-5-quinoxalin-6-yl-4,5-dihydropyrazol-1-yl]butan-1-one (PQDPB), 1-(3-phenyl-5-(quinoxalin-6-yl)-4,5-dihydro-1H-pyrazol-1-yl)propan-1-one (PQDPP), and 2-phenyl-1-[3-phenyl-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]ethanone (PPQDPE) has been investigated using electrochemical studies and quantum chemical calculations. The results showed that PQDPP is the best corrosion inhibitor among the three compounds studied and the inhibition efficiency increases with increase in concentration for all the inhibitors. The adsorption of inhibitor molecules on mild steel surface was found to be spontaneous and obeyed the Frumkin adsorption isotherm. Scanning electron microscopy (SEM) images confirmed the formation of protective films of the inhibitors on mild steel surface. Quantum chemical calculations showed that the inhibitors have the tendency to be protonated in the acid and the results agree with experimental ob...

Corrosion of magnesium alloys: the role of alloying

Abstract: The demand for light-weighting in transport and consumer electronics has seen rapid growth in the commercial usage of magnesium (Mg). The major use of Mg is now in cast Mg products, as opposed to the use of Mg as an alloying element in other alloy systems and there is an emerging market of wrought Mg products and biomedical Mg components – such that the past two decades have seen a significant number of new Mg-alloys reported. None-the-less, the corrosion of Mg alloys continues to be a challenge facing engineers seeking weight reductions by deployment of Mg. Herein, authors review the influence of alloying on the corrosion of Mg-alloys, with particular emphasis on the underlying electrochemical kinetics that dictate the ultimate corrosion rate. Such a review focusing on the chemistry–corrosion link, both in depth and in a holistic approach, is lacking. As such the authors do not describe aspects such as high-temperature oxidation or cracking, but focus on delivering the state-of-the-art with regar...

Density functional theory and molecular dynamics simulation study on corrosion inhibition performance of mild steel by mercapto-quinoline Schiff base corrosion inhibitor

Abstract: Corrosion inhibition mechanism of two mercapto-quinoline Schiff bases, eg., 3-((phenylimino)methyl)quinoline-2-thiol (PMQ) and 3-((5-methylthiazol-2-ylimino)methyl) quinoline-2-thiol (MMQT) on mild steel surface is investigated by quantum chemical calculation and molecular dynamics simulation. Quantum chemical parameters such as EHOMO, ELUMO, energy gap (ΔE), dipolemoment (µ), electronegativity (χ), global hardness (η) and fraction of electron transfers from the inhibitor molecule to the metallic atom surface (ΔN) have been studied to investigate their relative corrosion inhibition performance. Parameters like local reactive sites of the present molecule have been analyzed through Fukui indices. Moreover, adsorption behavior of the inhibitor molecules on Fe (1 1 0) surface have been analyzed using molecular dynamics simulation. The binding strength of the concerned inhibitor molecules on mild steel surface follows the order MMQT>PMQ, which is in good agreement with the experimentally determined inhibition efficiencies. In view of the above, our approach will be helpful for quick prediction of a potential inhibitor from a lot of similar inhibitors and subsequently in their rational designed synthesis for corrosion inhibition application following a wet chemical synthetic route.

Adsorption and corrosion inhibition effect of Schiff base molecules on the mild steel surface in 1 M HCl medium: a combined experimental and theoretical approach

Abstract: Corrosion inhibition performance of 2-(2-hydroxybenzylideneamino)phenol (L1), 2-(5-chloro-2-hydroxybenzylideneamino)phenol (L2) and 2-(2-hydroxy-5-nitrobenzylideneamino)phenol (L3) on the corrosion behaviour of mild steel surface in a 1 M hydrochloric acid (HCl) solution is investigated by sophisticated analytical methods like potentiodynamic polarization, electrochemical impedance spectroscopy and weight loss measurements. Polarization studies showed that all the compounds are mixed type (cathodic and anodic) inhibitors and the inhibition efficiency (η%) increased with increasing inhibitor concentration. The inhibition actions of these Schiff base molecules are discussed in view of blocking the electrode surface by means of adsorption of the inhibitor molecule obeying the Langmuir adsorption isotherm. Scanning electron microscopy (SEM) studies of the metal surfaces confirmed the existence of an adsorbed film. Density functional theory (DFT) and molecular dynamics (MD) simulation have been used to determine the relationship between molecular configuration and their inhibition efficiencies. The order of inhibition performance obtained from experimental results is successfully verified by DFT and MD simulation.

Extremely durable biofouling-resistant metallic surfaces based on electrodeposited nanoporous tungstite films on steel

Abstract: Formation of unwanted deposits on steels during their interaction with liquids is an inherent problem that often leads to corrosion, biofouling and results in reduction in durability and function. Here we report a new route to form anti-fouling steel surfaces by electrodeposition of nanoporous tungsten oxide (TO) films. TO-modified steels are as mechanically durable as bare steel and highly tolerant to compressive and tensile stresses due to chemical bonding to the substrate and island-like morphology. When inherently superhydrophilic TO coatings are converted to superhydrophobic, they remain non-wetting even after impingement with yttria-stabilized-zirconia particles, or exposure to ultraviolet light and extreme temperatures. Upon lubrication, these surfaces display omniphobicity against highly contaminating media retaining hitherto unseen mechanical durability. To illustrate the applicability of such a durable coating in biofouling conditions, we modified naval construction steels and surgical instruments and demonstrated significantly reduced marine algal film adhesion, Escherichia coli attachment and blood staining.

Advanced micro/nanocapsules for self-healing smart anticorrosion coatings

Abstract: Smart self-healing coatings for corrosion protection of metallic substrates (steel, magnesium, and aluminium, and their alloys) have attracted tremendous interest due to their capability to prevent crack propagation in the protective coatings by releasing active agents from micro/nanocapsules, that is, micro/nano particles consisting of a coating layer or a shell (micro/nanocontainers) and core material (solids, droplets of liquids or gases), in a controllable manner. This paper aims to give a concise review on the most recent advances in preparing micro/nanocapsules based on different types of micro/nanocontainers, i.e., organic polymer coatings, inorganic clays, mesoporous silica nanoparticles, polyelectrolyte multilayers, etc. for smart coatings with self-healing properties. The state-of-the-art design and preparation of micro/nanocapsules are highlighted with detailed examples.

Modelling of pitting corrosion in marine and offshore steel structures – A technical review

Abstract: Corrosion is a major cause of structural deterioration in marine and offshore structures. It affects the life of process equipment and pipelines, and can result in structural failure, leakage, product loss, environmental pollution and the loss of life. Pitting corrosion is regarded as one of the most hazardous forms of corrosion for marine and offshore structures. The total loss of the structure might be very small, but local rate of attack can be very large and can lead to early catastrophic failure. Pitting corrosion is a localized accelerated dissolution of metal that occurs as a result of a breakdown in the protective passive film on the metal surface. It has been studied for many years; however, the structural failure due to pit characteristics is still not fully understood. Accurate pit depth measurements, precise strength assessment techniques, risk analysis due to pitting, and the mathematical relationship of the environmental factors that causes pitting failure are also factors, which need further understanding. Hence this paper focuses on these issues. It reviews and analyses the current understanding of the pitting corrosion mechanism and investigates all possible factors that can cause pitting corrosion. Furthermore, different techniques employed by scientists and researchers to identify and model the pitting corrosion are also reviewed and analysed. Future work should involve an in-depth scientific study of the corrosion mechanism and an engineering predictive model is recommended in order to assess failure, and thereby attempt to increase the remaining life of offshore assets.

Corrosion of Zirconium Alloys Used for Nuclear Fuel Cladding

Abstract: During operation, nuclear fuel rods are immersed in the primary water, causing waterside corrosion and consequent hydrogen ingress. In this review, the mechanisms of corrosion and hydrogen pickup and the role of alloy selection in minimizing both phenomena are considered on the basis of two principal characteristics: the pretransition kinetics and the loss of oxide protectiveness at transition. In zirconium alloys, very small changes in composition or microstructure can cause significant corrosion differences so that corrosion performance is strongly alloy dependent. The alloys show different, but reproducible, subparabolic pretransition kinetics and transition thicknesses. A mechanism for oxide growth and breakup based on a detailed study of the oxide structure can explain these results. Through the use of the recently developed coupled current charge compensation model of corrosion kinetics and hydrogen pickup, the subparabolic kinetics and the hydrogen fraction can be rationalized: Hydrogen pickup incr...

Corrosion mechanism and hydrogen evolution on Mg

Abstract: Magnesium (Mg) dissolution is distinct from other engineering metals, as Mg can support cathodic hydrogen evolution on its surface during anodic polarisation. The phenomenon of cathodic hydrogen evolution upon anodically polarised Mg is characterised by the rate of the hydrogen evolution reaction (HER) increasing with anodic polarisation, a phenomenon called the negative different effect (NDE). Mg has a tendency to aggressively corrode in aqueous solutions, impairing its application as a durable engineering material or a predictable electrode material, which is also influenced by the NDE. Over the last century a number of different theories have sought to explain the NDE. However, recent progress in research upon Mg utilising contemporary methods including advanced electrochemical techniques, on-line elemental analysis and cross-sectional electron microscopy, have not only refined the understanding of Mg dissolution, but discredited almost a century of alternate theories. During anodic polarisation, a bilayered MgO/Mg(OH)2 film forms on Mg, appearing as a dark region on visual inspection. This film gradually occupies the bulk of the previously pristine Mg surface, and importantly sustains (and enhances) the HER. This phenomenon of cathodic activation may also be catalysed by an enrichment of noble elements or impurities on the Mg surface, which could play an important role in promoting the HER. A phenomenological model for the dissolution of Mg encompassing the current opinion of many researchers is presented herein.

Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts.

Abstract: In recent years, the oxygen evolution reaction (OER) has attracted increased research interest due to its crucial role in electrochemical energy conversion devices for renewable energy applications. The vast majority of OER catalyst materials investigated are metal oxides of various compositions. The experimental results obtained on such materials strongly suggest the existence of a fundamental and universal correlation between the oxygen evolution activity and the corrosion of metal oxides. This corrosion manifests itself in structural changes and/or dissolution of the material. We prove from basic thermodynamic considerations that any metal oxide must become unstable under oxygen evolution conditions irrespective of the pH value. The reason is the thermodynamic instability of the oxygen anion in the metal oxide lattice. Our findings explain many of the experimentally observed corrosion phenomena on different metal oxide OER catalysts.

High energy density rechargeable magnesium battery using earth-abundant and non-toxic elements

Abstract: Rechargeable magnesium batteries are poised to be viable candidates for large-scale energy storage devices in smart grid communities and electric vehicles. However, the energy density of previously proposed rechargeable magnesium batteries is low, limited mainly by the cathode materials. Here, we present new design approaches for the cathode in order to realize a high-energy-density rechargeable magnesium battery system. Ion-exchanged MgFeSiO4 demonstrates a high reversible capacity exceeding 300 mAh·g−1 at a voltage of approximately 2.4 V vs. Mg. Further, the electronic and crystal structure of ion-exchanged MgFeSiO4 changes during the charging and discharging processes, which demonstrates the (de)insertion of magnesium in the host structure. The combination of ion-exchanged MgFeSiO4 with a magnesium bis(trifluoromethylsulfonyl)imide–triglyme electrolyte system proposed in this work provides a low-cost and practical rechargeable magnesium battery with high energy density, free from corrosion and safety problems.

The dual role of microbes in corrosion

Abstract: Corrosion is the result of a series of chemical, physical and (micro) biological processes leading to the deterioration of materials such as steel and stone. It is a world-wide problem with great societal and economic consequences. Current corrosion control strategies based on chemically produced products are under increasing pressure of stringent environmental regulations. Furthermore, they are rather inefficient. Therefore, there is an urgent need for environmentally friendly and sustainable corrosion control strategies. The mechanisms of microbially influenced corrosion and microbially influenced corrosion inhibition are not completely understood, because they cannot be linked to a single biochemical reaction or specific microbial species or groups. Corrosion is influenced by the complex processes of different microorganisms performing different electrochemical reactions and secreting proteins and metabolites that can have secondary effects. Information on the identity and role of microbial communities that are related to corrosion and corrosion inhibition in different materials and in different environments is scarce. As some microorganisms are able to both cause and inhibit corrosion, we pay particular interest to their potential role as corrosion-controlling agents. We show interesting interfaces in which scientists from different disciplines such as microbiology, engineering and art conservation can collaborate to find solutions to the problems caused by corrosion.

Preparation of graphene oxide modified by titanium dioxide to enhance the anti-corrosion performance of epoxy coatings

Abstract: Solvent-based epoxy resins are often used for the anti-corrosion purpose but their cured process fabricating plentiful micro-pore via solvent evaporation is an intrinsic shortcoming and it is thus necessary to obstacle their micro-pore for enhancement antiseptic property. With the purpose of the enhancement, we synthesized TiO 2 –GO sheet hybrids using titanium dioxide loading on graphene oxide sheets with the help of 3-aminopropyltriethoxysilane, and dispersing the sheets into epoxy resin at a low weight fraction of 2%. The electrochemical impedance spectroscopy (EIS) test and monitoring coatings' morphology in corrosion process reveal that the corrosion resistant performance is significantly enhanced by the addition of TiO 2 –GO hybrids to epoxy. Comparisons with other nanofillers including TiO 2 and graphene oxide (GO) indicate that TiO 2 –GO hybrids exhibit an obvious superiority in enhancing the corrosion resistant of epoxy coatings at the same contents. The superiority of the TiO 2 –GO hybrids is related to their exfoliation, dispersion and excellent plugging micro-pore property arising from their laminated structure. Furthermore, the corrosion resistant mechanisms were tentatively proposed for the TiO 2 –GO/epoxy coatings.

Nanometre-scale evidence for interfacial dissolution-reprecipitation control of silicate glass corrosion.

Abstract: Silicate glasses are durable solids, and yet they are chemically unstable in contact with aqueous fluids-this has important implications for numerous industrial applications related to the corrosion resistance of glasses, or the biogeochemical weathering of volcanic glasses in seawater. The aqueous dissolution of synthetic and natural glasses results in the formation of a hydrated, cation-depleted near-surface alteration zone and, depending on alteration conditions, secondary crystalline phases on the surface. The long-standing accepted model of glass corrosion is based on diffusion-coupled hydration and selective cation release, producing a surface-altered zone. However, using a combination of advanced atomic-resolution analytical techniques, our data for the first time reveal that the structural and chemical interface between the pristine glass and altered zone is always extremely sharp, with gradients in the nanometre to sub-nanometre range. These findings support a new corrosion mechanism, interfacial dissolution-reprecipitation. Moreover, they also highlight the importance of using analytical methods with very high spatial and mass resolution for deciphering the nanometre-scale processes controlling corrosion. Our findings provide evidence that interfacial dissolution-reprecipitation may be a universal reaction mechanism that controls both silicate glass corrosion and mineral weathering.