Toward design of synergistically active carbon-based catalysts for electrocatalytic hydrogen evolution

Replacement of precious Pt catalyst with cost-effective alternatives would be significantly beneficial for hydrogen production via electrocatalytic hydrogen evolution reaction (HER). All candidates thus far are exclusively metallic catalysts, which suffer inherent corrosion and oxidation susceptibility during acidic proton-exchange membrane electrolysis. Herein, based on theoretical predictions, we designed and synthesized nitrogen (N) and phosphorus (P) dual-doped graphene as a nonmetallic electrocatalyst for sustainable and efficient hydrogen production. The N and P heteroatoms could coactivate the adjacent C atom in the graphene matrix by affecting its valence orbital energy levels to induce a synergistically enhanced reactivity toward HER. As a result, the dual-doped graphene showed higher electrocatalytic HER activity than single-doped ones and comparable performance to some of the traditional metallic catalysts.

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.

Factors affecting acceptability of an email-based intervention to increase fruit and vegetable consumption

 Background: Fresh Facts is a 30-day email-delivered intervention designed to increase the fruit and vegetable consumption of Australian young adults. This study investigated the extent to which the program was acceptable to members of the target audience and examined the relationships between participant and intervention characteristics, attrition, effectiveness, and acceptability ratings. Methods: Young adults were randomised to two levels of message frequency: high-frequency (n = 102), low-frequency (n = 173). Individuals in the high-frequency group received daily emails while individuals in the low-frequency group received an email every 3 days. Results: Individuals in the high-frequency group were more likely to indicate that they received too many emails than individuals in the low-frequency group. No other differences in acceptability were observed. Baseline beliefs about fruit and vegetables were an important predictor of intervention acceptability. In turn, acceptability was associated with a number of indicators of intervention success, including change in fruit and vegetable consumption. Conclusions: The findings highlight the importance of considering the relationship between these intervention and participant factors and acceptability in intervention design and evaluation. Results support the ongoing use of email-based interventions to target fruit and vegetable consumption within young adults. However, the relationships between beliefs about fruit and vegetable consumption and acceptability suggest that this intervention may be differentially effective depending on individual's existing beliefs about fruit and vegetable consumption. As such, there is a pressing need to consider these factors in future research in order to minimize attrition and maximize intervention effectiveness when interventions are implemented outside of a research context.

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.

An overview of new progresses in understanding pipeline corrosion

An approach to achieving the ambitious goal of cost effectively extending the safe operation life of energy pipeline to 100 years is the application of health monitoring and life prediction tools that are able to provide both long-term remnant pipeline life prediction and in-situ pipeline condition monitoring. A critical step is the enhancement of technological capabilities that are required for understanding and quantifying the effects of key factors influencing buried steel pipeline corrosion and environmentally assisted materials degradation, and the development of condition monitoring technologies that are able to provide in-situ monitoring and site-specific warning of pipeline damage. This paper provides an overview of our current research aimed at developing new sensors and electrochemical cells for monitoring, categorising and quantifying the level and nature of external pipeline and coating damages under the combined effects of various inter-related variables and processes such as localised corrosion, coating cracking and disbondment, cathodic shielding, transit loss of cathodic protection.

Monitoring cathodic shielding and corrosion under disbonded coatings

This work presents a novel corrosion monitoring probe designed for simulating the conditions developed under disbonded coatings and for measuring current densities and their distribution over a simulated pipeline surface. The probe’s concept was experimentally evaluated via immersion tests under Cathodic Protection (CP) in high resistivity aqueous solution. Under the disbonded area, anodic currents as well as cathodic currents were both measured. Anodic current densities were used to calculate metal losses by means of Faraday’s law. Calculated corrosion patterns were compared with corrosion damage observed at the probe’s surface after a period of test. The probe’s working principles are explained in terms of simple electrochemistry.

Weldability of duplex stainless steel

Duplex stainless steels (DSSs) have many advantages due to the unique structural combination of ferrite and austenite grains. The structural change of these materials is very complex during welding, and it deteriorates the functional properties. This research investigates different welding processes such as laser beam, resistance, tungsten inert gas, friction stir, submerged arc, and plasma arc weldings considering the research available in the literature. The welding mechanism, change of material structure, and control parameters have been analyzed for every welding process. This analysis clearly shows that DSS melts in all most all welding processes, but the thermal cycle and maximum heat input are different. This difference affects the resulting structure and functional properties of the weld significantly.

Yielding behaviour of martensite in steel

Although martensite is recognised as a very strong phase in carbon steels, its initial yielding commences at low stresses and the tensile stress-strain curve shows a smooth, rounded form. Evidence is presented from x-ray diffraction to show that this behaviour is due to the presence of intra-granular stresses that are residues after the shear transformation from austenite to martensite. These internal stresses are reduced in magnitude by plastic deformation and also by tempering. Reduction of internal stress due to plasticity is shown by a decrease in XRD line broadening after deformation. A simple model is presented in which the stress-strain behaviour is controlled by relaxation of the internal stresses almost up to the point of the ultimate tensile strength. It demonstrates that only a very small fraction of the material remaining in a purely elastic state provides a large stabilising effect resisting necking. A corollary of this is that the uniform elongation of martensitic steel actually increases with increase in the strength level. Effects of heat treatment are also reproduced in the model, including the increase in conventional yield stress (Rp0.2) that occurs after low temperature tempering.

Synergistic effects of sodium lauroyl sarcosinate and glutamic acid in inhibition assembly against copper corrosion in acidic solution

© 2015 Elsevier B.V. All rights reserved. A self-assembled multilayer (SAM) from sodium lauroyl sarcosinate (SLS) and glutamic acid (GLU) is formed on copper surface. Its inhibition ability against copper corrosion is examined by electrochemical analysis and weight loss test. In comparison to SAM formed by just SLS or GLU, a synergistic effect is observed when the coexistence of SLS and GLU in SAM. The SLS/GLU SAM has an acicular multilayer structure, and SAM prepared under the condition of 5 mM SLS and 1 mM GLU shows the best protection efficiency. PM6 calculation reveals that the synergistic effect stems from interactions between SLS, GLU and cupric ions.

Electrochemical impedance spectroscopy as a tool to measure cathodic disbondment on coated steel surfaces: capabilities and limitations

The disbondment of protective organic coatings under excessive cathodic protection potentials is a widely reported coating failure mechanism. Traditional methods of evaluating cathodic disbondment are based on ex situ visual inspection of coated metal surfaces after being exposed to standard cathodic disbondment testing conditions for a long period of time. Although electrochemical impedance spectroscopy (EIS) has been employed as an effective means of evaluating various anti-corrosion properties of organic coatings; its application for assessing the cathodic disbondment resistance of coatings has not been sufficiently exploited. This paper reports an experimental study aimed at developing EIS into a tool for in situ measurement and monitoring of cathodic disbondment of coatings. A clear correlation between EIS parameters and the disbonded coating areas has been confirmed upon short term exposure of epoxy-coated steel electrodes to cathodic disbondment conditions; however the degree of this correlation was found to decrease with the extension of exposure duration. This observation suggests that EIS loses its sensitivity with the propagation of coating disbondment, and that in order to achieve quantitative determination of the coating cathodic disbondment localized EIS measurements are required to measure the parameters related to local disbonded areas.

The restoration of the passivity of stainless steel Weldments in pickling solutions observed using electrochemical and surface analytical methods

In this study, a solution containing ammonium fluoride (NH4F) and nitric acid (HNO3) was used as an alternative to the conventional highly toxic pickling solution HF/HNO3 for pickling weldments of selected stainless steels including Type 316 stainless steel (UNS S31600), duplex stainless steel 2205 (UNS S32205), and super duplex stainless steel 2507 (UNS S32750). Electrochemical and surface analytical methods were used to understand the effects of pickling on the stainless steel weldments. Cyclic potentiodynamic polarization (CPP) test results indicated that the restoration of passivity of stainless steel weldments could be achieved by pickling the weldments in both HF/HNO3 solution and NH4F/HNO3 solutions. Scanning electron microscopy observation of the UNS S32750 weldment surface revealed that both the HF/HNO3 solution and the NH4F/HNO3 solution could remove the heat tint on the weldment. X-ray photoelectron spectroscopy analysis indicated that treatment in these two pickling solutions produced passive films with similar characteristics. Thus, this work suggests that the NH4F/HNO3 solution is a promising alternative to HF/HNO3 solution for the pickling of stainless steel weldments, and that the CPP test approach can be used in conjunction with surface analytical methods for further development of safer and environmentally friendly picklingsolutions.

Monitoring corrosion of reinforced concrete beams in a chloride containing environment under different loading levels

Corrosion has significant adverse effects on the durability of reinforced concrete (RC) structures, especially those exposed to a marine environment and subjected to mechanical stress, such as bridges, jetties, piers and wharfs. Previous studies have been carried out to investigate the corrosion behaviour of steel rebar in various concrete structures, however, few studies have focused on the corrosion monitoring of RC structures that are subjected to both mechanical stress and environmental effects. This paper presents an exploratory study on the development of corrosion monitoring and detection techniques for RC structures under the combined effects of external loadings and corrosive media. Four RC beams were tested in 3% NaCl solutions under different levels of point loads. Corrosion processes occurring on steel bars under different loads and under alternative wetting - drying cycle conditions were monitored. Electrochemical and microscopic methods were utilised to measure corrosion potentials of steel bars; to monitor galvanic currents flowing between different steel bars in each beam; and to observe corrosion patterns, respectively. The results indicated that steel corrosion in RC beams was affected by local stress. The point load caused the increase of galvanic currents, corrosion rates and corrosion areas. Pitting corrosion was found to be the main form of corrosion on the surface of the steel bars for most of the beams, probably due to the local concentration of chloride ions. In addition, visual observation of the samples confirmed that the localities of corrosion were related to the locations of steel bars in beams. It was also demonstrated that electrochemical devices are useful for the detection of RC beam corrosion.

The formation of ultrafine ferrite through static transformation in low carbon steels

A novel approach was used to produce an ultrafine grain structure in low carbon steels with a wide range of hardenability. This included warm deformation of supercooled austenite followed by reheating in the austenite region and cooling (RHA). The ultrafine ferrite structure was independent of steel composition. However, the mechanism of ferrite refinement changed with the steel quench hardenability. In a relatively low hardenable steel, the ultrafine structure was produced through dynamic strain induced transformation, whereas the ferrite refinement was formed by static transformation in steels with high quench hardenability. The use of a model Ni-30Fe austenitic alloy revealed that the deformation temperature has a strong effect on the nature of the intragranular defects. There was a transition temperature below which the cell dislocation structure changed to laminar microbands. It appears that the extreme refinement of ferrite is due to the formation of extensive high angle intragranular defects at these low deformation temperature that then act as sites for static transformation. © 2008 World Scientific Publishing Company.