Electrochemical comparison of IrO2 prepared by anodic oxidation of pure iridium and IrO2 prepared by thermal decomposition of H2IrCl6 precursor solution

Surface redox activities, oxygen evolution reaction (OER), oxidation of formic acid (FA), and anodic stability were investigated and compared for IrO₂ electrodes prepared by two techniques: the thermal decomposition of H₂IrCl₆ precursor (TDIROF) and the anodic oxidation of metallic iridium (AIROF). Surface redox activities involved on the AIROF were found to be much faster than those involved on the TDIROF. Concerning the oxygen evolution reaction, both films show a similar mechanism and specific electrocatalytic activities. The situation seems to be different for FA oxidation. In fact, on TDIROF, the oxidation of FA and the OER compete involving the same surface redox couple Ir(VI)/Ir(IV) contrary to FA oxidation on AIROF, where the Ir(V)/Ir(IV) surface redox couple is involved. Finally, electrode stability measurements have shown that contrary to TDIROF, which are very stable under anodic polarization, the AIROF are rapidly corroded under anodic treatment. This corrosion is enhanced even further in the presence of formic acid.     

EIS evaluation of the filiform corrosion of aluminium coated by a cataphoretic paint

Filiform corrosion is mainly considered as a cosmetic attack and is undesirable in most applications. The initiation and propagation of the filaments are related to different parameters such as the presence of defects, the permeability of the coating to water and oxygen, the adherence of the paint system and the presence of salts.

The aim of this work is to study the behaviour of painted aluminium samples towards filiform corrosion or delamination. The 6082 Aluminium alloy was selected and the samples were covered with a cataphoretic epoxy primer without lead (PPG Industries France). Prior to the application of the electrocoat, the samples were pre-treated by a commercial Zr/Ti or chromate conversion treatment or simply etched with a commercial acid etching product.

Filiform corrosion was studied by the normalized test (ISO/DIS 4623): painted and scratched samples were inoculated in HCl and exposed in a constant humidity chamber at 40 °C and 82% RH for 3 weeks. After exposure the samples were subjected to a visual and optical microscopic examination.

Electrochemical impedance spectroscopy was used to study the sensitivity to filiform corrosion. The operating mode of this test is similar to the normalized one. The samples were scratched before inoculation for 1 h in HCl and then exposed to the humidity chamber for a maximum of 4 days. The samples were tested by EIS in an acidified 0.1 M Na₂SO₄ electrolyte solution. The resulting impedance spectra were analyzed with an appropriate equivalent electrical circuit which allows the evaluation of the exposed metallic surface area, directly related to the extent of filiform corrosion or delamination. Different parameters were varied: the exposure time in the humidity chamber; the immersion time in the electrolyte sulphate solution as well as its pH and the coating thickness.     

Structure-property relationships for a series of polyimide copolymers with sulfonated pendant groups

A series of high molecular weight, sulfonated polyimide copolymers (8a-f) with controlled acid contents have been obtained using 2,2′-bis(4-sulfobenzyloxy)benzidine (14) prepared via a flexible synthetic route. This series of novel sulfonated polyimide membranes were found to possess higher hydrolytic stability than polyimides in which the sulfonic acid groups are bound directly to the polymer main chain. An in-depth analysis of conductivity data was also performed for 8 and compared to the results for Nafion^® (1), sulfonated poly(ether ether ketone) (2) and a main-chain sulfonated polyimide (3). In order to remove the influence of acid strength, the proton mobility value for 8 at infinite dilution was calculated and found to be 1.2(±0.6) × 10⁻³ cm² s⁻¹ V⁻¹. A catalyst-coated membrane (CCM)-MEA based on a polyimide incorporating 60% sulfonated monomer (8d) was found to exhibit comparable beginning-of-life fuel cell performance as a Nafion^®-based CCM MEA at 50 °C.     

Constrained Sintering of a Glass Ceramic Composite: I. Asymmetric Laminate

The camber of asymmetric laminates has been experimentally measured and predicted. Two cases are distinguished: (i) sintering of a viscous layer on a viscous substrate and (ii) sintering of a viscous layer on an elastic substrate. In the first case, particular attention is paid to the microstructure of the shrinking layer: a gradient in porosity as well as in pore size has been found along the thickness. Microstructural observations have been rationalized through an asymmetric stress state in the shrinking layer. In the second case, substrate cracking is predicted as function of Young's modulus and thickness ratio of the elastic substrate.     

In situ neutron diffraction measurement of strain relaxation in welds during heat treatment

Neutron diffraction (ND) is commonly used to investigate the stress redistribution before and after post-weld heat treatment (PWHT) in welded structures. However, there is a lack of information on the evaluations of strains during PWHT. The present work employed in situ ND to measure the relaxation of residual strains during conventional PWHT in multi-pass high-strength low-alloy steel welds. It was found that strain relaxation occurs principally during the heating stage of the heat treatment. The findings have important economic bearings and can be used to characterise comparable material combinations and optimise the PWHT process for high-strength low-alloy weld joints. This unique information also provides a valuable benchmark for the finite element modelling of this complex process.     

Some investigations into the optimal dimensional synthesis of parallel robots

In this paper, we will perform a comparison between two approaches of dimensional synthesis of parallel robots. The first one concerns the single-objective optimization approach; in this case, the dimensional synthesis is expressed by taking into account only one performance criterion but enables to get a final solution if it exists. The second one concerns the multi-objective optimization approach; it enables to simultaneously take into account several performance criteria. However, this approach appears to provide a set of solutions instead of a single expected final solution which should directly enable to carry out the structural synthesis. In fact, the search of a single final solution is postponed to a further step where the designers have to impose and/or restrict certain parameters. And we will establish if it is really necessary to make a multi-objective optimization approach or if a single-objective is sufficient to reach the objectives set in the specifications (user requirements). A discussion is proposed concerning the arising questions related to each approach and leading to the optimal dimensional synthesis. The PAR2 robot with two degree-of-freedom is used to exemplify the analysis and the comparison of the two approaches. The proposed comparison can be applied to any classes of parallel robots.     

Electrochemical surface nanopatterning by selective reductive desorption from mixed metal surfaces

We report on a novel strategy to the functionalisation of electrode surfaces based on the preparation and patterning of mixed metal electrodes using metal selective electrodesorption of a sacrificial alkanethiol. Plain palladium (Pd) and plain polycrystalline gold (poly-Au) electrodes were used initially to determine metal specific potential windows within which electrodesorption of the short alkanethiol mercaptoethanol could be achieved. We found that stripping of mercaptoethanol from gold was achieved at potentials lower than −0.800 V, whilst stripping from palladium was achieved at more positive potentials i.e. around −0.650 V. Mixed metal electrodes were prepared by electroplating for short period of times palladium onto poly-Au electrodes. The resulting surfaces were characterised electrochemically in 1 M H₂SO₄ and clearly exhibited reduction peaks for both gold and palladium oxide formation. The mixed metal electrodes were coated with mercaptoethanol, which was further selectively removed from Pd by cyclic voltammetry in NaOH in the Pd-specific potential window. The presence of bare Pd domains revealed following electrodesorption was confirmed by subsequently adsorbing the electroactive alkanethiol 6-ferrocenylhexanethiol onto the freshly revealed Pd. Cyclic voltamogramms exhibited sharp redox peaks that could only be attributed to the successful immobilisation of 6-ferrocenylhexanethiol onto fresh Pd domains. Control surfaces, i.e. MCE fully coated Pd/Poly-Au electrode, exposed to 6-ferrocenylhexanethiol did not exhibit significant voltammetric features, attesting to the efficient patterning of the mixed metal electrode by employing metal specific reductive desorption of short alkanethiols. The possibility to pattern electrode surfaces in such way will find application in the field of diagnostics, and also in heterogeneous catalysis where Pd-Au alloys have received an increased interest in the recent years.     

A new membrane bioreactor generation for wastewater treatment application: Strategy of membrane aeration management by sequencing aeration cycles

Polymem is developing in the past few years a new membrane bioreactor concept using external module membranes. The membranes are hollow fibers. They are housed in carters and work in outside/in filtration mode. Permanent air scouring is provided at the bottom of the module to control the accumulation of sludge on the membrane surface. In other words, the membrane carters look like bubble columns with hollow fiber membranes inside.The main advantages of this concept are the easy maintenance of the external modules; the total independence of the bioreactor from the membrane filtration part, which facilitates plant retrofitting and upgrading; the high membrane compacity (up to 500 m²/m3), and better efficiency of membrane air scouring thanks to a dedicated coarse bubbles aeration system inside the module vessel.The first part of this paper deals with the quantification of the specific aeration demand of the system. Aeration demand was compared to conventional MBR systems. The study shows that with this optimised geometry of module concept, the aeration flow rate is lowered compared with conventional processes.In the second part of this paper, an optimisation of the aeration demand was carried out by sequencing the cycle of aeration by incorporating a syncope in the aeration. Ratios of the time-on and time-off from 1/2 to 1/5 were tested for various instantaneous aeration flow rates. Impacts on both short term fouling and long term fouling were evaluated and quantified in terms of permeability decrease. The advantages of the location of the membrane in an external cylindrical carter have been demonstrated in terms of operating cost savings with a reduction of specific aeration demand for membranes scouring at 100 to 250 Nl/h m², which is half the classical consumption of the submerged MBR today.     

High-Fat Diet Aggravates Cerebral Infarct,Hemorrhagic Transformation and Neuroinflammation in a Mouse Stroke Model

Background: Stroke in context of type 2 diabetes (T2D) is associated with a poorer outcome than in non-diabetic conditions. We aimed at creating a new reproducible mouse model of stroke in impaired glucose tolerance conditions induced by high-fat diet. Methods: Adult C57BL6 mice were fed for 2 months with either normal diet (ND) or high-fat diet (HFD). We used a model of Middle Cerebral Artery Occlusion (MCAO) for 90 min. Oral Glucose Tolerance Test (OGTT) and Insulin Tolerance Test (ITT) were used to assess pre-diabetic status. Brain infarct volume, hemorrhagic transformation (HT) as well as systemic and cerebral inflammatory markers were evaluated. Results: HFD was associated with an increased body weight and glycemia following OGTT. The HFD group presented a significant increase in brain infarct volume (38.7 (IQR 30–46.7%) vs. 28.45 (IQR 21–30%); p = 0.016) and HT (HFD: 2 (IQR 1–5) vs. ND: 0 (IQR 0–1); p = 0.012) and higher levels of IL-6 and MCP-1 in infarcted hemisphere compared to the ND group. Conclusion: Two months of HFD in adult mice were sufficient to alter the lipid profile and the control of hyperglycemia. These metabolic perturbations were significantly associated with increased infarct volume and hemorrhagic complications.