Corrosion of mg alloy ZE41 and its mitigation using ionic liquids

Magnesium alloy ZE41 (Mg-Zn-RE-Zr), which is used extensively in the aerospace industry, possesses excellent mechanical properties albeit poor corrosion resistance. This work investigates the mechanism of corrosion, and the interaction between the grain boundary intermetallic phases, the zirconium (Zr)-rich regions within the grains and the bulk Mg rich matrix in both the as-cast and heat-treated conditions. The results of optical and scanning electron microscopy (SEM) show the importance of the microstructure in the initiation and propagation of corrosion in an aqueous environment. The Zr-rich regions play a distinct role in the early stages of corrosion with this alloy. The second part of this work investigates the interaction of two different ionic liquids (ILs) with the surface of the ZE41 alloy. ILs based on trihexyltetradecylphosphonium (P 6,6,6,14) coupled with either diphenylphosphate (DPP) or bis(trifluoromethanesulfonyl) amide (Tf 2N) have been shown to react with Mg alloy surfaces, leading to the formation of a surface film that can improve the corrosion resistance of the alloy. The interaction of the ILs with the ZE41 surface has been investigated by optical microscopy and SEM. Surface characterization has been performed using Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS). The surface characterization and microscopy revealed the preferential interaction with the grain boundaries and grain boundary phases. Thus the morphology and microstructure of the Mg surface seems critical in determining the nature of the interaction with the IL. The corrosion protection of the IL films formed on the ZE41 surface was investigated by SEM and potentiodynamic polarisation.

Synergistic effects of IAP inhibitor LCL161 and paclitaxel on hepatocellular carcinoma cells

Inhibitor of Apoptosis Proteins (IAPs) are key regulators of apoptosis in hepatocellular carcinoma (HCC) and their expression is negatively correlated with patient survival. LCL161 is a small molecule inhibitor of IAPs that has potent antitumour activity in a range of solid tumours. In HCC, response to LCL161 therapy has shown to be mediated by Bcl-2 expression. In this study, we aim to determine whether LCL161 has any therapeutic potential in HCC. Protein expression was determined by Western blot. Cell proliferation was determined by Cell Proliferation ELISA and BrdU colorimetric assays. Apoptosis was determined by Annexin V assay. Cell cycle analysis was performed by staining cells with propidium iodide and analysed in a FACScan. Automated Cell Counter and phase contrast microscopy were used to determine the cell viability. We have found that LCL161 targets (cIAP1, cIAP2 and XIAP) were up-regulated in HCC tumours. Both high Bcl-2 expressing HuH7 cells and low Bcl-2 expressing SNU423 cells showed strong resistance to LCL161 therapy with significant effects on both apoptosis and cell viability only evident at LCL161 concentrations of ⩾100μM. At these doses there was significant inhibition of IAP targets, however there was also significant inhibition of off-target proteins including pERK and pJNK suggesting apoptosis caused by drug toxicity. However, when used in combination with paclitaxel in HuH7 and SNU423 cells, LCL161 had significant antiproliferative effects at doses as low as 2μM and this was independent of Bcl-2 expression. Thus, LCL161 may be a useful agent in combination with paclitaxel to treat liver tumours.

Evaluating the corrosion behaviour of magnesium alloy in simulated biological fluid by using SECM to detect hydrogen evolution

Scanning electrochemical microscopy (SECM) in surface generation/tip collection mode is investigated as an assessment tool for studying the corrosion behaviour of magnesium in simulated biological fluid. The technique provides a local map of hydrogen (H2) evolution which alone can be used as a direct measure of corrosion. The H2 generated during corrosion of magnesium is oxidized at the probe(i.e. a Pt ultra micro-electrode);with the magnitude of the current generated due to oxidation being indicative of the intensity of H2 evolution at a local scale on the magnesium surface. This method was calibrated using a cathodically polarized Pt disk to simulate H2 evolution in a controlled condition on a homogeneous surface. Potential interference from dissolving Mg or high local pH was also investigated. The technique was implemented for studying H2 evolution at the surface of AZ31 as a model Mg alloy.SECM results combined with SEM-EDX and profilometry data revealed that local domains of higher H2 evolution on the surface of AZ31 are in close proximityof the observed pitting sites.

A five-gene hedgehog signature developed as a patient preselection tool for hedgehog inhibitor therapy in medulloblastoma

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Applications of scanning electrochemical microscopy (SECM) for local characterization of AZ31 surface during corrosion in a buffered media

Different modes of scanning electrochemical mapping (SECM) such as surface generation/tip collection (SG/TC), amperometry, AC-SECM and potentiometry were employed to characterize the active/passive domains, hydrogen gas (H2) evolution and local pH on a corroding surface of AZ31 in simulated biological fluid (SBF). It was found that the main domains of H2 evolution are associated with lower insulating properties of the surface as well as higher local pH. The near surface pH was found to be highly alkaline indicating that, even in a buffered solution such as SBF, the local pH on a corroding AZ31 surface can be significantly different to the bulk pH. © 2014 Elsevier Ltd.

Corrosion monitoring under disbonded coatings

Localized corrosion can occur under disbonded coatings threatening the safe operation of industry infrastructures such as underground oil and gas pipelines. Currently the assessment of localised corrosion under coating defects is a major technical challenge. The application of corrosion probes to monitor corrosion under disbonded coating also remains a difficulty. This paper presents a new corrosion sensor concept capable of electrochemically measuring corrosion rates under disbonded coatings on cathodically protected structures such as energy pipelines. Examples of its capabilities are illustrated with experimental data obtained in low conductivity aqueous solutions.

A review of techniques for the monitoring of cathodic shielding and corrosion under disbonded coatings

The mitigation of external corrosion of energy pipelines by a combination of barrier coatings and Cathodic Protection (CP) is not always effective. Even when design specifications are properly met, the shielding of cathodic protection current from reaching steel surface by disbonded barrier coatings, often referred to as cathodic shielding, may lead to severe corrosion problems such as deep pitting, high and near neutral pH Stress Corrosion Cracking (SCC) and Microbiologically Induced Corrosion (MIC). Unfortunately, current indirect assessment methods used in the pipeline industry have serious difficulties in detecting such corrosion problems. This paper provides a brief review of current techniques and their limitations when being applied under complex buried pipeline environmental conditions. The main purpose is to identify potential methods that could be utilised in the design of new monitoring probes specific for the monitoring of cathodic shielding and corrosion of disbonded coatings in the pipeline industry.

An overview of methods for simulating and evaluating pipeline corrosion

Steel pipelines, buried under the soil and protected by the combination of protective coatings and cathodic protection (CP), are used for oil and gas transportation. These pipelines are one of the critical infrastructures for energy transportation and therefore became lifelines of modern society. The deterioration of the external surfaces of transmission pipelines is a serious problem and is caused mainly by coating and/or CP failure leading to the loss of integrity of pipelines. To avoid such damage, there is a need of techniques which are able to locate active corrosion sites, monitor corrosion, and evaluate corrosion damage. Fundamental understanding of such processes occurring on coated pipelines (with various types of defects in coatings as well as pipe) in complex soil environment is necessary for the development of such techniques. Numerous laboratory techniques, i.e., electrochemical impedance spectroscopy based, polarisation measurements based, mathematical simulations, direct observation etc. have been used to develop fundamental understanding, simulate and evaluate corrosion occurring in oil and gas pipelines under various operating conditions. Given the complex nature of the pipeline corrosion, application of these laboratory techniques in field measurements as well as in understanding the corrosion mechanisms is lacking. This paper presents an overview of investigations, based on electrochemical techniques, for simulation and evaluation of pipeline corrosion in laboratory.

An electrochemical method for measuring localized corrosion under cathodic protection

 A new method has been developed to measure metal corrosion rates and their distribution under cathodic protection (CP). This method uses an electrochemically integrated multi-electrode array to take local measurements of cathodic current density while simulating a continuous metallic surface. The distribution of cathodic current densities obtained under CP was analyzed to estimate the anodic current component at each electrode of the array. Corrosion patterns determined by this new method have shown good correlation with visual inspection and surface profilometry of the multi-electrode array surface.

Effects of alloying elements on the corrosion behavior and biocompatibility of biodegradable magnesium alloys: a review

Magnesium (Mg) based alloys have been extensively considered for their use as biodegradable implant materials. However, controlling their corrosion rate in the physiological environment of the human body is still a significant challenge. One of the most effective approaches to address this challenge is to carefully select alloying compositions with enhanced corrosion resistance and mechanical properties when designing the Mg alloys. This paper comprehensively reviews research progress on the development of Mg alloys as biodegradable implant materials, highlighting the effects of alloying elements including aluminum (Al), calcium (Ca), lithium (Li), manganese (Mn), zinc (Zn), zirconium (Zr), strontium (Sr) and rare earth elements (REEs) on the corrosion resistance and biocompatibility of Mg alloys, from the viewpoint of the design and utilization of Mg biomaterials. The REEs covered in this review include cerium (Ce), erbium (Er), lanthanum (La), gadolinium (Gd), neodymium (Nd) and yttrium (Y). The effects of alloying elements on the microstructure, corrosion behavior and biocompatibility of Mg alloys have been critically summarized based on specific aspects of the physiological environment, namely the electrochemical effect and the biological behavior. This journal is © the Partner Organisations 2014.

The effect of treatment temperature on corrosion resistance and hydrophilicity of an ionic liquid coating for mg-based stents

Mg alloys are attractive candidate materials for biodegradable stents. However, there are few commercially available Mg-based stents in clinical use because Mg alloys generally undergo rapid localized corrosion in the body. In this study, we report a new surface coating for Mg alloy AZ31 based on a low-toxicity ionic liquid (IL), tributyl(methyl)phosphonium diphenyl phosphate (P1,4,4,4 dpp), to control its corrosion rate. Emphasis is placed on the effect of treatment temperature. We showed that enhancing the treatment temperature provided remarkable improvements in the performances of both corrosion resistance and biocompatibility. Increasing treatment temperature resulted in a thicker (although still nanometer scale) and more homogeneous IL film on the surface. Scanning electron microscopy and optical profilometry observations showed that there were many large, deep pits formed on the surface of bare AZ31 after 2 h of immersion in simulated body fluid (SBF). The IL coating (particularly when formed at 100 °C for 1 h) significantly suppressed the formation of these pits on the surface, making corrosion occur more uniformly. The P1,4,4,4 dpp IL film formed at 100 °C was more hydrophilic than the bare AZ31 surface, which was believed to be beneficial for avoiding the deposition of the proteins and cells on the surface and therefore improving the biocompatibility of AZ31 in blood. The interaction mechanism between this IL and AZ31 was also investigated using ATR-FTIR, which showed that both anion and cation of this IL were present in the film, and there was a chemical interaction between dpp(-) anion and the surface of AZ31 during the film formation.

The influence of rare earth mercaptoacetate on the initiation of corrosion on AA2024-T3 Part II: The influence of intermetallic compositions within heavily attacked sites

Localised corrosion is typical on AA2024-T3 due to intermetallic particles embedded in the alloy. The effect of intermetallic compositions on corrosion are not yet fully understood. EPMA data on AA2024-T3 surfaces before and after a 16. min immersion, analyses the influence of intermetallic clustering on the severity attack at local sites. While sites with a high number of domains and a large S-phase surface area typically lead to severe attack, maximising these features did not always lead to severe corrosion attack. Cerium or praseodymium mercaptoacetate inhibited corrosion ring formation. The common trends observed from such attack sites was also discussed.