Search results for: nickel electrode

Authors: Mehran Nozari-Asbemarz, Italo Pisano, Simin Arshi, Edmond Magner, James J. Leahy

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Integrating electrolytic synthesis with renewable energy makes it feasible to address urgent environmental and energy challenges. Conventional water electrolyzers concurrently produce H₂ and O₂, demanding additional procedures in gas separation to prevent contamination of H₂ with O₂. Moreover, the oxygen evolution reaction (OER), which is sluggish and has a low overall energy conversion efficiency, does not deliver a significant value product on the electrode surface. Compared to conventional water electrolysis, integrating electrolytic hydrogen generation from water with thermodynamically more advantageous aqueous organic oxidation processes can increase energy conversion efficiency and create value-added compounds instead of oxygen at the anode. One strategy is to use renewable and sustainable carbon sources from biomass, which has a large annual production capacity and presents a significant opportunity to supplement carbon sourced from fossil fuels. Numerous catalytic techniques have been researched in order to utilize biomass economically. Because of its safe operating conditions, excellent energy efficiency, and reasonable control over production rate and selectivity using electrochemical parameters, electrocatalytic upgrading stands out as an appealing choice among the numerous biomass refinery technologies. Therefore, we propose a broad framework for coupling H2 generation from water splitting with oxidative biomass upgrading processes. Four representative biomass targets were considered for oxidative upgrading that used a hierarchically porous CoFe-MOF/LDH @ Graphite Paper bifunctional electrocatalyst, including glucose, ethanol, benzyl, furfural, and 5-hydroxymethylfurfural (HMF). The potential required to support 50 mA cm-2 is considerably lower than (~ 380 mV) the potential for OER. All four compounds can be oxidized to yield liquid byproducts with economic benefit. The electrocatalytic oxidation of glucose to the value-added products, gluconic acid, glucuronic acid, and glucaric acid, was examined in detail. The cell potential for combined H₂ production and glucose oxidation was substantially lower than for water splitting (1.44 V(RHE) vs. 1.82 V(RHE) for 50 mA cm-2). In contrast, the oxidation byproduct at the anode was significantly more valuable than O₂, taking advantage of the more favorable glucose oxidation in comparison to the OER. Overall, such a combination of HER and oxidative biomass valorization using electrocatalysts prevents the production of potentially explosive H₂/O₂mixtures and produces high-value products at both electrodes with lower voltage input, thereby increasing the efficiency and activity of electrocatalytic conversion.

Keywords: biomass, electrocatalytic, glucose oxidation, hydrogen evolution

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Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

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Solid-state lithium metal batteries (SSLMBs) are considered promising candidates for next-generation energy storage devices due to their superior energy density and excellent safety. However, recent findings have shown that the formation of lithium (Li) dendrites in SSLMBs still exhibits a terrible growth ability, which makes the development of SSLMBs have to face the challenges posed by the Li dendrite problem. In this work, an inorganic/organic mixture coating material (g-C3N4/ZIF-8/PVDF) was used to modify the surface of lithium metal anode (LMA). Then the modified LMA (denoted as g-C₃N₄@Li) was assembled with lithium nafion (LiNf) coated commercial NCM811 (LiNf@NCM811) using a bilayer hybrid solid electrolyte (Bi-HSE) that incorporated 20 wt.% (vs. polymer) LiNf coated Li6.05Ga0.25La3Zr2O11.8F0.2 ([email protected]) filler faced to the positive electrode and the other layer with 80 wt.% (vs. polymer) filler content faced to the g-C₃N₄@Li. The garnet-type Li6.05Ga0.25La3Zr2O11.8F0.2 (LG0.25LZOF) solid electrolyte was prepared via co-precipitation reaction process from Taylor flow reactor and modified using lithium nafion (LiNf), a Li-ion conducting polymer. The Bi-HSE exhibited high ionic conductivity of 6.8  10–4 S cm–1 at room temperature, and a wide electrochemical window (0–5.0 V vs. Li/Li+). The coin cell was charged between 2.8 to 4.5 V at 0.2C and delivered an initial specific discharge capacity of 194.3 mAh g–1 and after 100 cycles it maintained 81.8% of its initial capacity at room temperature. The presence of a nano-sheet g-C3N4/ZIF-8/PVDF as a composite coating material on the LMA surface suppress the dendrite growth and enhance the compatibility as well as the interfacial contact between anode/electrolyte membrane. The g-C3N4@Li symmetrical cells incorporating this hybrid electrolyte possessed excellent interfacial stability over 1000 h at 0.1 mA cm–2 and a high critical current density (1 mA cm–2). Moreover, the in-situ formation of Li3N on the solid electrolyte interface (SEI) layer as depicted from the XPS result also improves the ionic conductivity and interface contact during the charge/discharge process. Therefore, these novel multi-layered fabrication strategies of hybrid/composite solid electrolyte membranes and modification of the LMA surface using mixed coating materials have potential applications in the preparation of highly safe high-voltage cathodes for SSLMBs.

Keywords: high-voltage cathodes, hybrid solid electrolytes, garnet, graphitic-carbon nitride (g-C3N4), ZIF-8 MOF

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Authors: Alan N. A. Heberle, Salatiel W. Da Silva, Valentin Perez-Herranz, Andrea M. Bernardes

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Contaminants of emerging concern are substances widely used, such as pharmaceutical products. These compounds represent risk for both wild and human life since they are not completely removed from wastewater by conventional wastewater treatment plants. In the environment, they can be harm even in low concentration (µ or ng/L), causing bacterial resistance, endocrine disruption, cancer, among other harmful effects. One of the most common taken medicine to treat cardiocirculatory diseases is the Atenolol (ATL), a β-Blocker, which is toxic to aquatic life. In this way, it is necessary to implement a methodology, which is capable to promote the degradation of the ATL, to avoid the environmental detriment. A very promising technology is the advanced electrochemical oxidation (AEO), which mechanisms are based on the electrogeneration of reactive radicals (mediated oxidation) and/or on the direct substance discharge by electron transfer from contaminant to electrode surface (direct oxidation). The hydroxyl (HO•) and sulfate (SO₄•⁻) radicals can be generated, depending on the reactional medium. Besides that, at some condition, the peroxydisulfate (S₂O₈²⁻) ion is also generated from the SO₄• reaction in pairs. Both radicals, ion, and the direct contaminant discharge can break down the molecule, resulting in the degradation and/or mineralization. However, ATL molecule and byproducts can still remain in the treated solution. On this wise, some efforts can be done to implement the AEO process, being one of them the use of a cationic membrane to separate the cathodic (reduction) from the anodic (oxidation) reactor compartment. The aim of this study is investigate the influence of the implementation of a cationic membrane (Nafion®-117) to separate both cathodic and anodic, AEO reactor compartments. The studied reactor was a filter-press, with bath recirculation mode, flow 60 L/h. The anode was an Nb/BDD2500 and the cathode a stainless steel, both bidimensional, geometric surface area 100 cm². The solution feeding the anodic compartment was prepared with ATL 100 mg/L using Na₂SO₄ 4 g/L as support electrolyte. In the cathodic compartment, it was used a solution containing Na₂SO₄ 71 g/L. Between both solutions was placed the membrane. The applied currents densities (iₐₚₚ) of 5, 20 and 40 mA/cm² were studied over 240 minutes treatment time. Besides that, the ATL decay was analyzed by ultraviolet spectroscopy (UV/Vis). The mineralization was determined performing total organic carbon (TOC) in TOC-L CPH Shimadzu. In the cases without membrane, the iₐₚₚ 5, 20 and 40 mA/cm² resulted in 55, 87 and 98 % ATL degradation at the end of treatment time, respectively. However, with membrane, the degradation, for the same iₐₚₚ, was 90, 100 and 100 %, spending 240, 120, 40 min for the maximum degradation, respectively. The mineralization, without membrane, for the same studied iₐₚₚ, was 40, 55 and 72 %, respectively at 240 min, but with membrane, all tested iₐₚₚ reached 80 % of mineralization, differing only in the time spent, 240, 150 and 120 min, for the maximum mineralization, respectively. The membrane increased the ATL oxidation, probably due to avoid oxidant ions (S₂O₈²⁻) reduction on the cathode surface.

Keywords: contaminants of emerging concern, advanced electrochemical oxidation, atenolol, cationic membrane, double compartment reactor

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Authors: Ali H. Daraji, Ye Jianqiao

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The micro electrical devices of the wireless sensor network are continuously developed and become very small and compact with low electric power requirements using limited period life conventional batteries. The low power requirement for these devices, cost of conventional batteries and its replacement have encouraged researcher to find alternative power supply represented by energy harvesting system to provide an electric power supply with infinite period life. In the last few years, the investigation of energy harvesting for structure health monitoring has increased to powering wireless sensor network by converting waste mechanical vibration into electricity using piezoelectric sensors. Optimisation of energy harvesting is an important research topic to ensure a flowing of efficient electric power from structural vibration. The harvesting power is mainly based on the properties of piezoelectric material, dimensions of piezoelectric sensor, its position on a structure and value of an external electric load connected between sensor electrodes. Larger surface area of sensor is not granted larger power harvesting when the sensor area is covered positive and negative mechanical strain at the same time. Thus lead to reduction or cancellation of piezoelectric output power. Optimisation of energy harvesting is achieved by locating these sensors precisely and efficiently on the structure. Limited published work has investigated the energy harvesting for aircraft wing. However, most of the published studies have simplified the aircraft wing structure by a cantilever flat plate or beam. In these studies, the optimisation of energy harvesting was investigated by determination optimal value of an external electric load connected between sensor electrode terminals or by an external electric circuit or by randomly splitting piezoelectric sensor to two segments. However, the aircraft wing structures are complex than beam or flat plate and mostly constructed from flat and curved skins stiffened by stringers and ribs with more complex mechanical strain induced on the wing surfaces. This aircraft wing structure bonded with discrete macro fibre composite sensors was modelled using multiphysics finite element to optimise the energy harvesting by determination of the optimal number of sensors, location and the output resistance load. The optimal number and location of macro fibre sensors were determined based on the maximization of the open and close loop sensor output voltage using frequency response analysis. It was found different optimal distribution, locations and number of sensors bounded on the top and the bottom surfaces of the aircraft wing.

Keywords: energy harvesting, optimisation, sensor, wing

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Authors: Masood Otarod, Ronald M. Supkowski

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This abstract discusses a method that reduces the general dispersion model in cylindrical coordinates to a second order linear ordinary differential equation with constant coefficients so that it can be utilized to conduct kinetic studies in packed bed tubular catalytic reactors at a broad range of Reynolds numbers. The model was tested by 13CO isotope transient tracing of the CO adsorption of Boudouard reaction in a differential reactor at an average Reynolds number of 0.2 over Pd-Al2O3 catalyst. Detailed experimental results have provided evidence for the validity of the theoretical framing of the model and the estimated parameters are consistent with the literature. The solution of the general dispersion model requires the knowledge of the radial distribution of axial velocity. This is not always known. Hence, up until now, the implementation of the dispersion model has been largely restricted to the plug-flow regime. But, ideal plug-flow is impossible to achieve and flow regimes approximating plug-flow leave much room for debate as to the validity of the results. The reduction of the general dispersion model transpires as a result of the application of a factorization theorem. Factorization theorem is derived from the observation that a cross section of a catalytic bed consists of a solid phase across which the reaction takes place and a void or porous phase across which no significant measure of reaction occurs. The disparity in flow and the heterogeneity of the catalytic bed cause the concentration of reacting compounds to fluctuate radially. These variabilities signify the existence of radial positions at which the radial gradient of concentration is zero. Succinctly, factorization theorem states that a concentration function of axial and radial coordinates in a catalytic bed is factorable as the product of the mean radial cup-mixing function and a contingent dimensionless function. The concentration of adsorbed compounds are also factorable since they are piecewise continuous functions and suffer the same variability but in the reverse order of the concentration of mobile phase compounds. Factorability is a property of packed beds which transforms the general dispersion model to an equation in terms of the measurable mean radial cup-mixing concentration of the mobile phase compounds and mean cross-sectional concentration of adsorbed species. The reduced model does not require the knowledge of the radial distribution of the axial velocity. Instead, it is characterized by new transport parameters so denoted by Ωc, Ωa, Ωc, and which are respectively denominated convection coefficient cofactor, axial dispersion coefficient cofactor, and radial dispersion coefficient cofactor. These cofactors adjust the dispersion equation as compensation for the unavailability of the radial distribution of the axial velocity. Together with the rest of the kinetic parameters they can be determined from experimental data via an optimization procedure. Our data showed that the estimated parameters Ωc, Ωa Ωr, are monotonically correlated with the Reynolds number. This is expected to be the case based on the theoretical construct of the model. Computer generated simulations of methanation reaction on nickel provide additional support for the utility of the newly conceptualized dispersion model.

Keywords: factorization, general dispersion model, isotope transient kinetic, partial differential equations

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Authors: Hsyi-En Cheng, Ying-Yi Liou

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Metal-oxide semiconductor (MOS) gas sensors are widely used in the gas-detection market due to their high sensitivity, fast response, and simple device structures. However, the high working temperature of MOS gas sensors makes them difficult to integrate with the appliance or consumer goods. One-dimensional (1-D) nanostructures are considered to have the potential to lower their working temperature due to their large surface-to-volume ratio, confined electrical conduction channels, and small feature sizes. Unfortunately, the difficulty of fabricating 1-D nanostructure electrodes has hindered the development of low-temperature MOS gas sensors. In this work, we proposed a method to fabricate nanotube-arrays, and the SnO₂ nanotube-array sensors with different wall thickness were successfully prepared and examined. The fabrication of SnO₂ nanotube arrays incorporates the techniques of barrier-free anodic aluminum oxide (AAO) template and atomic layer deposition (ALD) of SnO₂. First, 1.0 µm Al film was deposited on ITO glass substrate by electron beam evaporation and then anodically oxidized by five wt% phosphoric acid solution at 5°C under a constant voltage of 100 V to form porous aluminum oxide. As the Al film was fully oxidized, a 15 min over anodization and a 30 min post chemical dissolution were used to remove the barrier oxide at the bottom end of pores to generate a barrier-free AAO template. The ALD using reactants of TiCl4 and H₂O was followed to grow a thin layer of SnO₂ on the template to form SnO₂ nanotube arrays. After removing the surface layer of SnO₂ by H₂ plasma and dissolving the template by 5 wt% phosphoric acid solution at 50°C, upright standing SnO₂ nanotube arrays on ITO glass were produced. Finally, Ag top electrode with line width of 5 μm was printed on the nanotube arrays to form SnO₂ nanotube-array sensor. Two SnO₂ nanotube-arrays with wall thickness of 30 and 60 nm were produced in this experiment for the evaluation of gas sensing ability. The flat SnO₂ films with thickness of 30 and 60 nm were also examined for comparison. The results show that the properties of ALD SnO₂ films were related to the deposition temperature. The films grown at 350°C had a low electrical resistivity of 3.6×10-3 Ω-cm and were, therefore, used for the nanotube-array sensors. The carrier concentration and mobility of the SnO₂ films were characterized by Ecopia HMS-3000 Hall-effect measurement system and were 1.1×1020 cm-3 and 16 cm3/V-s, respectively. The electrical resistance of SnO₂ film and nanotube-array sensors in air and in a 5% H₂-95% N₂ mixture gas was monitored by Pico text M3510A 6 1/2 Digits Multimeter. It was found that, at 200 °C, the 30-nm-wall SnO₂ nanotube-array sensor performs the highest responsivity to 5% H₂, followed by the 30-nm SnO₂ film sensor, the 60-nm SnO₂ film sensor, and the 60-nm-wall SnO₂ nanotube-array sensor. However, at temperatures below 100°C, all the samples were insensitive to the 5% H₂ gas. Further investigation on the sensors with thinner SnO₂ is necessary for improving the sensing ability at temperatures below 100 °C.

Keywords: atomic layer deposition, nanotube arrays, gas sensor, tin dioxide

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Authors: Hilal Köse, Şeyma Dombaycıoğlu, Ali Osman Aydın, Hatem Akbulut

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Rechargeable lithium-ion batteries (LIBs) have become promising power sources for a wide range of applications, such as mobile communication devices, portable electronic devices and electrical/hybrid vehicles due to their long cycle life, high voltage and high energy density. Graphite, as anode material, has been widely used owing to its extraordinary electronic transport properties, large surface area, and high electrocatalytic activities although its limited specific capacity (372 mAh g-1) cannot fulfil the increasing demand for lithium-ion batteries with higher energy density. To settle this problem, many studies have been taken into consideration to investigate new electrode materials and metal oxide/graphene composites are selected as a kind of promising material for lithium ion batteries as their specific capacities are much higher than graphene. Among them, SnO₂, an n-type and wide band gap semiconductor, has attracted much attention as an anode material for the new-generation lithium-ion batteries with its high theoretical capacity (790 mAh g-1). However, it suffers from large volume changes and agglomeration associated with the Li-ion insertion and extraction processes, which brings about failure and loss of electrical contact of the anode. In addition, there is also a huge irreversible capacity during the first cycle due to the formation of amorphous Li₂O matrix. To obtain high capacity anode materials, we studied on the synthesis and characterization of SnO₂-Graphene nanocomposites and investigated the capacity of this free-standing anode material in this work. For this aim, firstly, graphite oxide was obtained from graphite powder using the method described by Hummers method. To prepare the nanocomposites as free-standing anode, graphite oxide particles were ultrasonicated in distilled water with SnO2 nanoparticles (1:1, w/w). After vacuum filtration, the GO-SnO₂ paper was peeled off from the PVDF membrane to obtain a flexible, free-standing GO paper. Then, GO structure was reduced in hydrazine solution. Produced SnO2- graphene nanocomposites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), and X-ray diffraction (XRD) analyses. CR2016 cells were assembled in a glove box (MBraun-Labstar). The cells were charged and discharged at 25°C between fixed voltage limits (2.5 V to 0.2 V) at a constant current density on a BST8-MA MTI model battery tester with 0.2C charge-discharge rate. Cyclic voltammetry (CV) was performed at the scan rate of 0.1 mVs-1 and electrochemical impedance spectroscopy (EIS) measurements were carried out using Gamry Instrument applying a sine wave of 10 mV amplitude over a frequency range of 1000 kHz-0.01 Hz.

Keywords: SnO₂-graphene, nanocomposite, anode, Li-ion battery

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Authors: Igor B. Sivaev

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Design of molecular machines is an extraordinary growing and very important area of research that it was recognized by awarding Sauvage, Stoddart and Feringa the Nobel Prize in Chemistry in 2016 'for the design and synthesis of molecular machines'. Based on the type of motion being performed, molecular machines can be divided into two main types: molecular motors and molecular switches. Molecular switches are molecules or supramolecular complexes having bistability, i.e., the ability to exist in two or more stable forms, among which may be reversible transitions under external influence (heating, lighting, changing the medium acidity, the action of chemicals, exposure to magnetic or electric field). Molecular switches are the main structural element of any molecular electronics devices. Therefore, the design and the study of molecules and supramolecular systems capable of performing mechanical movement is an important and urgent problem of modern chemistry. There is growing interest in molecular switches and other devices of molecular electronics based on transition metal complexes; therefore choice of suitable stable organometallic unit is of great importance. An example of such unit is bis(dicarbollide) complexes of transition metals [3,3’-M(1,2-C₂B₉H₁₁)₂]ⁿ⁻. The control on the ligand rotation in such complexes can be reached by introducing substituents which could provide stabilization of certain rotamers due to specific interactions between the ligands, on the one hand, and which can participate as Lewis bases in complex formation with external metals resulting in a change in the rotation angle of the ligands, on the other hand. A series of isomeric methyl sulfide derivatives of cobalt bis(dicarbollide) complexes containing methyl sulfide substituents at boron atoms in different positions of the pentagonal face of the dicarbollide ligands [8,8’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻, rac-[4,4’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ and meso-[4,7’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ were synthesized by the reaction of CoCl₂ with the corresponding methyl sulfide carborane derivatives [10-MeS-7,8-C₂B₉H₁₁)₂]⁻ and [10-MeS-7,8-C₂B₉H₁₁)₂]⁻. In the case of asymmetrically substituted cobalt bis(dicarbollide) complexes the corresponding rac- and meso-isomers were successfully separated by column chromatography as the tetrabutylammonium salts. The compounds obtained were studied by the methods of ¹H, ¹³C, and ¹¹B NMR spectroscopy, single crystal X-ray diffraction, cyclic voltammetry, controlled potential coulometry and quantum chemical calculations. It was found that in the solid state, the transoid- and gauche-conformations of the 8,8’- and 4,4’-isomers are stabilized by four intramolecular CH···S(Me)B hydrogen bonds each one (2.683-2.712 Å and 2.709-2.752 Å, respectively), whereas gauche-conformation of the 4,7’-isomer is stabilized by two intramolecular CH···S hydrogen bonds (2.699-2.711 Å). The existence of the intramolecular CH·S(Me)B hydrogen bonding in solutions was supported by the 1H NMR spectroscopy. These data are in a good agreement with results of the quantum chemical calculations. The corresponding iron and nickel complexes were synthesized as well. The reaction of the methyl sulfide derivatives of cobalt bis(dicarbollide) with various labile transition metal complexes results in rupture of intramolecular hydrogen bonds and complexation of the methyl sulfide groups with external metal. This results in stabilization of other rotational conformation of cobalt bis(dicarbollide) and can be used in design of molecular switches. This work was supported by the Russian Science Foundation (16-13-10331).

Keywords: molecular switches, NMR spectroscopy, single crystal X-ray diffraction, transition metal bis(dicarbollide) complexes, quantum chemical calculations

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Authors: Akmez Nabeerasool, Michaelis Massaros, Nigel Brown, David Sanderson, David Parocki, Charlotte Thompson, Mike Lodge, Mikael Khan

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The provision of clean and safe drinking water is of paramount importance and is a basic human need. Water scarcity coupled with tightening of regulations and the inability of current treatment technologies to deal with emerging contaminants and Pharmaceuticals and personal care products means that alternative treatment technologies that are viable and cost effective are required in order to meet demand and regulations for clean water supplies. Logistically, the application of water treatment in rural areas presents unique challenges due to the decentralisation of abstraction points arising from low population density and the resultant lack of infrastructure as well as the need to treat water at the site of use. This makes it costly to centralise treatment facilities and hence provide potable water direct to the consumer. Furthermore, across the UK there are segments of the population that rely on a private water supply which means that the owner or user(s) of these supplies, which can serve one household to hundreds, are responsible for the maintenance. The treatment of these private water supply falls on the private owners, and it is imperative that a chemical free technological solution that can operate unattended and does not produce any waste is employed. Arvia’s patented advanced oxidation technology combines the advantages of adsorption and electrochemical regeneration within a single unit; the Organics Destruction Cell (ODC). The ODC uniquely uses a combination of adsorption and electrochemical regeneration to destroy organics. Key to this innovative process is an alternative approach to adsorption. The conventional approach is to use high capacity adsorbents (e.g. activated carbons with high porosities and surface areas) that are excellent adsorbents, but require complex and costly regeneration. Arvia’s technology uses a patent protected adsorbent, Nyex™, which is a non-porous, highly conductive, graphite based adsorbent material that enables it to act as both the adsorbent and as a 3D electrode. Adsorbed organics are oxidised and the surface of the Nyex™ is regenerated in-situ for further adsorption without interruption or replacement. Treated water flows from the bottom of the cell where it can either be re-used or safely discharged. Arvia™ Technology Ltd. has trialled the application of its tertiary water treatment technology in treating reservoir water abstracted near Glasgow, Scotland, with promising results. Several other pilot plants have also been successfully deployed at various locations in the UK showing the suitability and effectiveness of the technology in removing recalcitrant organics (including pharmaceuticals, steroids and hormones), COD and colour.

Keywords: Arvia™ process, adsorption, water treatment, electrochemical oxidation

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Authors: Malory Jonata

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Chlordecone (CLD) is an organochlorine pesticide used between 1971 and 1993 in both Guadeloupe and Martinique for the control of banana black weevil. The bishomocubane structure which characterizes this chemical compound led to high stability in organic matter and high persistence in the environment. Recently, researchers found that CLD can be degraded by isolated bacteria consortiums and, particularly, by bacteria such as Citrobacter sp 86 and Delsulfovibrio sp 86. Actually, six transformation product families of CLD are known. Moreover, the latest discovery showed that CLD was disappearing faster than first predicted in highly contaminated soil in Guadeloupe. However, the toxicity of transformation products is still unknown, and knowledge has to be deepened on the degradation ways and chemical characteristics of chlordecone and its transformation products. Microbial fuel cells (MFC) are electrochemical systems that can convert organic matter into electricity thanks to electroactive bacteria. These bacteria can exchange electrons through their membranes to solid surfaces or molecules. MFC have proven their efficiency as bioremediation systems in water and soils. They are already used for the bioremediation of several organochlorine compounds such as perchlorate, trichlorophenol or hexachlorobenzene. In this study, a three-electrodes system, inspired by MFC, is used to try to degrade chlordecone using bacteria from a mangrove swamp in Martinique. As we know, some mangrove bacteria are electroactive. Furthermore, the CLD rate seems to decline in mangrove swamp sediments. This study aims to prove that electroactive bacteria from a mangrove swamp in Martinique can degrade CLD thanks to a three-electrodes bioelectrochemical system. To achieve this goal, the tree-electrodes assembly has been connected to a potentiostat. The substrate used is mangrove water and sediments sampled in the mangrove swamp of La Trinité, a coastal city in Martinique, where CLD contamination has already been studied. Electroactive biofilms are formed by imposing a potential relative to Saturated Calomel Electrode using chronoamperometry. Moreover, their comportment has been studied by using cyclic voltametry. Biofilms have been studied under different imposed potentials, several conditions of the substrate and with or without CLD. In order to quantify the evolution of CLD rates in the substrate’s system, gas chromatography coupled with mass spectrometry (GC-MS) was performed on pre-treated samples of water and sediments after short, medium and long-term contact with the electroactive biofilms. Results showed that between -0,8V and -0,2V, the three-electrodes system was able to reduce the chemical in the substrate solution. The first GC-MS analysis result of samples spiked with CLD seems to reveal decreased CLD concentration over time. In conclusion, the designed bioelectrochemical system can provide the necessary conditions for chlordecone degradation. However, it is necessary to improve three-electrodes control settings in order to increase degradation rates. The biological pathways are yet to enlighten by biologicals analysis of electroactive biofilms formed in this system. Moreover, the electrochemical study of mangrove substrate gives new informations on the potential use of this substrate for bioremediation. But further studies are needed to a better understanding of the electrochemical potential of this environment.

Keywords: bioelectrochemistry, bioremediation, chlordecone, mangrove swamp

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Authors: Ching Shya Lee, Mohamed Kheireddine Aroua, Wan Mohd Ashri Wan Daud, Patrick Cognet, Yolande Peres, Mohammed Ajeel

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In recent years, with the decreasing supply of fossil fuel, renewable energy has received a significant demand. Biodiesel which is well known as vegetable oil based fatty acid methyl ester is an alternative fuel for diesel. It can be produced from transesterification of vegetable oils, such as palm oil, sunflower oil, rapeseed oil, etc., with methanol. During the transesterification process, crude glycerol is formed as a by-product, resulting in 10% wt of the total biodiesel production. To date, due to the fast growing of biodiesel production in worldwide, the crude glycerol supply has also increased rapidly and resulted in a significant price drop for glycerol. Therefore, extensive research has been developed to use glycerol as feedstock to produce various added-value chemicals, such as tartronic acid, mesoxalic acid, glycolic acid, glyceric acid, propanediol, acrolein etc. The industrial processes that usually involved are selective oxidation, biofermentation, esterification, and hydrolysis. However, the conversion of glycerol into added-value compounds by electrochemical approach is rarely discussed. Currently, the approach is mainly focused on the electro-oxidation study of glycerol under potentiostatic mode for cogenerating energy with other chemicals. The electro-organic synthesis study from glycerol under galvanostatic mode is seldom reviewed. In this study, the glycerol was converted into various added-value compounds by electrochemical method under galvanostatic mode. This work aimed to study the possible compounds produced from glycerol by electrochemical technique in a one-pot electrolysis cell. The electro-organic synthesis study from glycerol was carried out in a single compartment reactor for 8 hours, over the platinum cathode and anode electrodes under acidic condition. Various parameters such as electric current (1.0 A to 3.0 A) and reaction temperature (27 °C to 80 °C) were evaluated. The products obtained were characterized by using gas chromatography-mass spectroscopy equipped with an aqueous-stable polyethylene glycol stationary phase column. Under the optimized reaction condition, the glycerol conversion achieved as high as 95%. The glycerol was successfully converted into various added-value chemicals such as ethylene glycol, glycolic acid, glyceric acid, acetaldehyde, formic acid, and glyceraldehyde; given the yield of 1%, 45%, 27%, 4%, 0.7% and 5%, respectively. Based on the products obtained from this study, the reaction mechanism of this process is proposed. In conclusion, this study has successfully converted glycerol into a wide variety of added-value compounds. These chemicals are found to have high market value; they can be used in the pharmaceutical, food and cosmetic industries. This study effectively opens a new approach for the electrochemical conversion of glycerol. For further enhancement on the product selectivity, electrode material is an important parameter to be considered.

Keywords: biodiesel, glycerol, electrochemical conversion, galvanostatic mode

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Authors: S. Maniruzzaman, N. Ramanujam, Qazi Akhter Rasool, Swapan Kumar Biswas, P. Prasad, Chandrakanta Ojha

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Landslide is one of the major natural disasters in South Asian countries. Applying 2D Electrical Resistivity Tomographic Imaging estimation of geometry, thickness, and depth of failure zone of the landslide can be made. Landslide is a pertinent problem in Nilgris plateau next to Himalaya. Nilgris range consists of hard Archean metamorphic rocks. Intense weathering prevailed during the Pre-Cambrian time had deformed the rocks up to 45m depth. The landslides are dominant in the southern and eastern part of plateau of is comparatively smaller than the northern drainage basins, as it has low density of drainage; coarse texture permitted the more of infiltration of rainwater, whereas in the northern part of the plateau entombed with high density of drainage pattern and fine texture with less infiltration than run off, and low to the susceptible to landslide. To get comprehensive information about the landslide zone 2D Electrical Resistivity Tomographic imaging study with CRM 500 Resistivity meter are used in Coonoor– Mettupalyam sector of Nilgiris plateau. To calculate Factor of Safety the infinite slope model of Brunsden and Prior is used. Factor of Safety can be expressed (FS) as the ratio of resisting forces to disturbing forces. If FS < 1 disturbing forces are larger than resisting forces and failure may occur. The geotechnical parameters of soil samples are calculated on the basis upon the apparent resistivity values for litho units of measured from 2D ERT image of the landslide zone. Relationship between friction angles for various soil properties is established by simple regression analysis from apparent resistivity data. Increase of water content in slide zone reduces the effectiveness of the shearing resistance and increase the sliding movement. Time-lapse resistivity changes to slope failure is determined through geophysical Factor of Safety which depends on resistivity and site topography. This ERT technique infers soil property at variable depths in wider areas. This approach to retrieve the soil property and overcomes the limit of the point of information provided by rain gauges and porous probes. Monitoring of slope stability without altering soil structure through the ERT technique is non-invasive with low cost. In landslide prone area an automated Electrical Resistivity Tomographic Imaging system should be installed permanently with electrode networks to monitor the hydraulic precursors to monitor landslide movement.

Keywords: 2D ERT, landslide, safety factor, slope stability

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Authors: M. Lehtihet, S. Rosado, C. Pradère, J. Leng

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Poly(3,4-ethylene dioxythiophene) polystyrene sulfonate (PEDOT: PSS), is a polymer mixture well-known for its semiconducting properties and is widely used in the coating industry for its visible transparency and high electronic conductivity (up to 4600 S/cm) as a transparent non-metallic electrode and in organic light-emitting diodes (OLED). It also possesses strong absorption properties in the Near Infra-Red (NIR) range (λ ranging between 900 nm to 2.5 µm). In the present work, we take advantage of this absorption to explore its potential use as a transparent light-to-heat converter. PEDOT: PSS aqueous dispersions are deposited onto a glass substrate using a blade-coating technique in order to produce uniform coatings with controlled thicknesses ranging in ≈ 400 nm to 2 µm. Blade-coating technique allows us good control of the deposit thickness and uniformity by the tuning of several experimental conditions (blade velocity, evaporation rate, temperature, etc…). This liquid coating technique is a well-known, non-expensive technique to realize thin film coatings on various substrates. For coatings on glass substrates destined to solar insulation applications, the ideal coating would be made of a material able to transmit all the visible range while reflecting the NIR range perfectly, but materials possessing similar properties still have unsatisfactory opacity in the visible too (for example, titanium dioxide nanoparticles). NIR absorbing thin films is a more realistic alternative for such an application. Under solar illumination, PEDOT: PSS thin films heat up due to absorption of NIR light and thus act as planar heaters while maintaining good transparency in the visible range. Whereas they screen some NIR radiation, they also generate heat which is then conducted into the substrate that re-emits this energy by thermal emission in every direction. In order to quantify the heating power of these coatings, a sample (coating on glass) is placed in a black enclosure and illuminated with a solar simulator, a lamp emitting a calibrated radiation very similar to the solar spectrum. The temperature of the rear face of the substrate is measured in real-time using thermocouples and a black-painted Peltier sensor measures the total entering flux (sum of transmitted and re-emitted fluxes). The heating power density of the thin films is estimated from a model of the thin film/glass substrate describing the system, and we estimate the Solar Heat Gain Coefficient (SHGC) to quantify the light-to-heat conversion efficiency of such systems. Eventually, the effect of additives such as dimethyl sulfoxide (DMSO) or optical scatterers (particles) on the performances are also studied, as the first one can alter the IR absorption properties of PEDOT: PSS drastically and the second one can increase the apparent optical path of light within the thin film material.

Keywords: PEDOT: PSS, blade-coating, heat, thin-film, Solar spectrum

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Authors: Panagiotis Svarnas, Polykarpos Papadopoulos

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Atmospheric-pressure cold plasmas continue to gain increasing interest for various applications due to their unique properties, like cost-efficient production, high chemical reactivity, low gas temperature, adaptability, etc. Numerous designs have been proposed for these plasmas production in terms of electrode configuration, driving voltage waveform and working gas(es). However, in order to exploit most of the advantages of these systems, the majority of the designs are based on dielectric-barrier discharges (DBDs) either in filamentary or glow regimes. A special category of the DBD-based atmospheric-pressure cold plasmas refers to the so-called plasma jets, where a carrier noble gas is guided by the dielectric barrier (usually a hollow cylinder) and left to flow up to the atmospheric air where a complicated hydrodynamic interplay takes place. Although it is now well established that these plasmas are generated due to ionizing waves reminding in many ways streamer propagation, they exhibit discrete characteristics which are better mirrored on the terms 'guided streamers' or 'plasma bullets'. These 'bullets' travel with supersonic velocities both inside the dielectric barrier and the channel formed by the noble gas during its penetration into the air. The present work is devoted to the interpretation of the electro-hydrodynamic effects that take place downstream of the dielectric barrier opening, i.e., in the noble gas-air mixing area where plasma bullet propagate under the influence of local electric fields in regions of variable noble gas concentration. Herein, we focus on the role of the local space charge and the residual ionic charge left behind after the bullet propagation in the gas flow field modification. The study communicates both experimental and numerical results, coupled in a comprehensive manner. The plasma bullets are here produced by a custom device having a quartz tube as a dielectric barrier and two external ring-type electrodes driven by sinusoidal high voltage at 10 kHz. Helium gas is fed to the tube and schlieren photography is employed for mapping the flow field downstream of the tube orifice. Mixture mass conservation equation, momentum conservation equation, energy conservation equation in terms of temperature and helium transfer equation are simultaneously solved, leading to the physical mechanisms that govern the experimental results. Namely, we deal with electro-hydrodynamic effects mainly due to momentum transfer from atomic ions to neutrals. The atomic ions are left behind as residual charge after the bullet propagation and gain energy from the locally created electric field. The electro-hydrodynamic force is eventually evaluated.

Keywords: atmospheric-pressure plasmas, dielectric-barrier discharges, schlieren photography, electro-hydrodynamic force

Procedia PDF Downloads 138

Authors: Krzysztof Skiba, Zbigniew Czyz, Ksenia Siadkowska, Piotr Borowiec

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The article presents selected concepts of technologies that use intelligent materials in aircraft in order to improve their performance. Most of the research focuses on solutions that improve the performance of fixed wing aircraft due to related to their previously dominant market share. Recently, the development of the rotorcraft has been intensive, so there are not only helicopters but also gyroplanes and unmanned aerial vehicles using rotors and vertical take-off and landing. There are many different technologies to change a shape of the aircraft or its elements. Piezoelectric, deformable actuator systems can be applied in the system of an active control of vibration dampening in the aircraft tail structure. Wires made of shape memory alloys (SMA) could be used instead of hydraulic cylinders in the rear part of the aircraft flap. The aircraft made of intelligent materials (piezoelectrics and SMA) is one of the NASA projects which provide the possibility of changing a wing shape coefficient by 200%, a wing surface by 50%, and wing deflections by 20 degrees. Active surfaces made of shape memory alloys could be used to control swirls in the flowing stream. An intelligent control system for helicopter blades is a method for the active adaptation of blades to flight conditions and the reduction of vibrations caused by the rotor. Shape memory alloys are capable of recovering their pre-programmed shapes. They are divided into three groups: nickel-titanium-based, copper-based, and ferromagnetic. Due to the strongest shape memory effect and the best vibration damping ability, a Ni-Ti alloy is the most commercially important. The subject of this work was to prepare a conceptual design of a rotor blade with SMA actuators. The scope of work included 3D design of the supporting rotor blade, 3D design of beams enabling to change the geometry by changing the angle of rotation and FEM (Finite Element Method) analysis. The FEM analysis was performed using NX 12 software in the Pre/Post module, which includes extended finite element modeling tools and visualizations of the obtained results. Calculations are presented for two versions of the blade girders. For FEM analysis, three types of materials were used for comparison purposes (ABS, aluminium alloy 7057, steel C45). The analysis of internal stresses and extreme displacements of crossbars edges was carried out. The internal stresses in all materials were close to the yield point in the solution of girder no. 1. For girder no. 2 solution, the value of stresses decreased by about 45%. As a result of the displacement analysis, it was found that the best solution was the ABS girder no. 1. The displacement of about 0.5 mm was obtained, which resulted in turning the crossbars (upper and lower) by an angle equal to 3.59 degrees. This is the largest deviation of all the tests. The smallest deviation was obtained for beam no. 2 made of steel. The displacement value of the second girder solution was approximately 30% lower than the first solution. Acknowledgement: This work has been financed by the Polish National Centre for Research and Development under the LIDER program, Grant Agreement No. LIDER/45/0177/L-9/17/NCBR/2018.

Keywords: aircraft, helicopters, shape memory alloy, SMA, smart material, unmanned aerial vehicle, UAV

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Authors: Reyna Singh, David Lokhat, Milan Carsky

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The world crude oil demand is projected to rise to 108.5 million bbl/d by the year 2035. With reserves estimated at 869 billion tonnes worldwide, coal is an abundant resource. This work was aimed at producing a high value hydrocarbon liquid product from the Direct Coal Liquefaction (DCL) process at, comparatively, mild operating conditions. Via hydrogenation, the temperature-staged approach was investigated. In a two reactor lab-scale pilot plant facility, the objectives included maximising thermal dissolution of the coal in the presence of a hydrogen donor solvent in the first stage, subsequently promoting hydrogen saturation and hydrodesulphurization (HDS) performance in the second. The feed slurry consisted of high grade, pulverized bituminous coal on a moisture-free basis with a size fraction of < 100μm; and Tetralin mixed in 2:1 and 3:1 solvent/coal ratios. Magnetite (Fe3O4) at 0.25wt% of the dry coal feed was added for the catalysed runs. For both stages, hydrogen gas was used to maintain a system pressure of 100barg. In the first stage, temperatures of 250℃ and 300℃, reaction times of 30 and 60 minutes were investigated in an agitated batch reactor. The first stage liquid product was pumped into the second stage vertical reactor, which was designed to counter-currently contact the hydrogen rich gas stream and incoming liquid flow in the fixed catalyst bed. Two commercial hydrotreating catalysts; Cobalt-Molybdenum (CoMo) and Nickel-Molybdenum (NiMo); were compared in terms of their conversion, selectivity and HDS performance at temperatures 50℃ higher than the respective first stage tests. The catalysts were activated at 300°C with a hydrogen flowrate of approximately 10 ml/min prior to the testing. A gas-liquid separator at the outlet of the reactor ensured that the gas was exhausted to the online VARIOplus gas analyser. The liquid was collected and sampled for analysis using Gas Chromatography-Mass Spectrometry (GC-MS). Internal standard quantification methods for the sulphur content, the BTX (benzene, toluene, and xylene) and alkene quality; alkanes and polycyclic aromatic hydrocarbon (PAH) compounds in the liquid products were guided by ASTM standards of practice for hydrocarbon analysis. In the first stage, using a 2:1 solvent/coal ratio, an increased coal to liquid conversion was favoured by a lower operating temperature of 250℃, 60 minutes and a system catalysed by magnetite. Tetralin functioned effectively as the hydrogen donor solvent. A 3:1 ratio favoured increased concentrations of the long chain alkanes undecane and dodecane, unsaturated alkenes octene and nonene and PAH compounds such as indene. The second stage product distribution showed an increase in the BTX quality of the liquid product, branched chain alkanes and a reduction in the sulphur concentration. As an HDS performer and selectivity to the production of long and branched chain alkanes, NiMo performed better than CoMo. CoMo is selective to a higher concentration of cyclohexane. For 16 days on stream each, NiMo had a higher activity than CoMo. The potential to cover the demand for low–sulphur, crude diesel and solvents from the production of high value hydrocarbon liquid in the said process, is thus demonstrated.

Keywords: catalyst, coal, liquefaction, temperature-staged

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Authors: Laura C. Loaiza, Elodie Salager, Nicolas Louvain, Athmane Boulaoued, Antonella Iadecola, Patrik Johansson, Lorenzo Stievano, Vincent Seznec, Laure Monconduit

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Lithium-ion batteries (LIBs) have an important place among energy storage devices due to their high capacity and good cyclability. However, the advancements in portable and transportation applications have extended the research towards new horizons, and today the development is hampered, e.g., by the capacity of the electrodes employed. Silicon and germanium are among the considered modern anode materials as they can undergo alloying reactions with lithium while delivering high capacities. It has been demonstrated that silicon in its highest lithiated state can deliver up to ten times more capacity than graphite (372 mAh/g): 4200 mAh/g for Li₂₂Si₅ and 3579 mAh/g for Li₁₅Si₄, respectively. On the other hand, germanium presents a capacity of 1384 mAh/g for Li₁₅Ge₄, and a better electronic conductivity and Li ion diffusivity as compared to Si. Nonetheless, the commercialization potential of Ge is limited by its cost. The synergetic effect of Si₁₋ₓGeₓ alloys has been proven, the capacity is increased compared to Ge-rich electrodes and the capacity retention is increased compared to Si-rich electrodes, but the exact performance of this type of electrodes will depend on factors like specific capacity, C-rates, cost, etc. There are several reports on various formulations of Si₁₋ₓGeₓ alloys with promising LIB anode performance with most work performed on complex nanostructures resulting from synthesis efforts implying high cost. In the present work, we studied the electrochemical mechanism of the Si₀.₅Ge₀.₅ alloy as a realistic micron-sized electrode formulation using carboxymethyl cellulose (CMC) as the binder. A combination of a large set of in situ and operando techniques were employed to investigate the structural evolution of Si₀.₅Ge₀.₅ during lithiation and delithiation processes: powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), Raman spectroscopy, and 7Li solid state nuclear magnetic resonance spectroscopy (NMR). The results have presented a whole view of the structural modifications induced by the lithiation/delithiation processes. The Si₀.₅Ge₀.₅ amorphization was observed at the beginning of discharge. Further lithiation induces the formation of a-Liₓ(Si/Ge) intermediates and the crystallization of Li₁₅(Si₀.₅Ge₀.₅)₄ at the end of the discharge. At really low voltages a reversible process of overlithiation and formation of Li₁₅₊δ(Si₀.₅Ge₀.₅)₄ was identified and related with a structural evolution of Li₁₅(Si₀.₅Ge₀.₅)₄. Upon charge, the c-Li₁₅(Si₀.₅Ge₀.₅)₄ was transformed into a-Liₓ(Si/Ge) intermediates. At the end of the process an amorphous phase assigned to a-SiₓGey was recovered. Thereby, it was demonstrated that Si and Ge are collectively active along the cycling process, upon discharge with the formation of a ternary Li₁₅(Si₀.₅Ge₀.₅)₄ phase (with a step of overlithiation) and upon charge with the rebuilding of the a-Si-Ge phase. This process is undoubtedly behind the enhanced performance of Si₀.₅Ge₀.₅ compared to a physical mixture of Si and Ge.

Keywords: lithium ion battery, silicon germanium anode, in situ characterization, X-Ray diffraction

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Authors: Oscar Bareiro, Johannes Sackmann, Thomas Gries

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Carbon fiber reinforced polymer composites (CFRP) are used in a wide variety of applications due to its advantageous properties and design versatility. The braiding process enables the manufacture of components with good toughness and fatigue strength. However, failure mechanisms of CFRPs are complex and still present challenges associated with their maintenance and repair. Within the broad scope of structural health monitoring (SHM), strain monitoring can be applied to composite materials to improve reliability, reduce maintenance costs and safely exhaust service life. Traditional SHM systems employ e.g. fiber optics, piezoelectrics as sensors, which are often expensive, time consuming and complicated to implement. A cost-efficient alternative can be the exploitation of the conductive properties of fiber-based sensors such as carbon, copper, or constantan - a copper-nickel alloy – that can be utilized as sensors within composite structures to achieve strain monitoring. This allows the structure to provide feedback via electrical signals to a user which are essential for evaluating the structural condition of the structure. This work presents a strategy for the in-process integration of resistance-based sensors (Elektrisola Feindraht AG, CuNi23Mn, Ø = 0.05 mm) into textile preforms during its manufacture via the braiding process (Herzog RF-64/120) to achieve strain monitoring of braided composites. For this, flat samples of instrumented composite laminates of carbon fibers (Toho Tenax HTS40 F13 24K, 1600 tex) and epoxy resin (Epikote RIMR 426) were manufactured via vacuum-assisted resin infusion. These flat samples were later cut out into test specimens and the integrated sensors were wired to the measurement equipment (National Instruments, VB-8012) for data acquisition during the execution of mechanical tests. Quasi-static tests were performed (tensile, 3-point bending tests) following standard protocols (DIN EN ISO 527-1 & 4, DIN EN ISO 14132); additionally, dynamic tensile tests were executed. These tests were executed to assess the sensor response under different loading conditions and to evaluate the influence of the sensor presence on the mechanical properties of the material. Several orientations of the sensor with regards to the applied loading and sensor placements inside the laminate were tested. Strain measurements from the integrated sensors were made by programming a data acquisition code (LabView) written for the measurement equipment. Strain measurements from the integrated sensors were then correlated to the strain/stress state for the tested samples. From the assessment of the sensor integration approach it can be concluded that it allows for a seamless sensor integration into the textile preform. No damage to the sensor or negative effect on its electrical properties was detected during inspection after integration. From the assessment of the mechanical tests of instrumented samples it can be concluded that the presence of the sensors does not alter significantly the mechanical properties of the material. It was found that there is a good correlation between resistance measurements from the integrated sensors and the applied strain. It can be concluded that the correlation is of sufficient accuracy to determinate the strain state of a composite laminate based solely on the resistance measurements from the integrated sensors.

Keywords: braiding process, in-process sensor integration, instrumented composite material, resistance-based sensor, strain monitoring

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Authors: Mikko Salminen, Niklas Ravaja

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Emotional intelligence (EI) consists of skills for monitoring own emotions and emotions of others, skills for discriminating different emotions, and skills for using this information in thinking and actions. EI enhances, for example, work outcomes and organizational climate. We suggest that the role and manifestations of EI should also be studied in real leadership situations, especially during the emotional, social interaction. Leadership is essentially a process to influence others for reaching a certain goal. This influencing happens by managerial processes and computer-mediated communication (e.g. e-mail) but also by face-to-face, where facial expressions have a significant role in conveying emotional information. Persons with high EI are typically perceived more positively, and they have better social skills. We hypothesize, that during social interaction high EI enhances the ability to detect other’s emotional state and controlling own emotional expressions. We suggest, that emotionally intelligent leader’s experience less stress during social leadership situations, since they have better skills in dealing with the related emotional work. Thus the high-EI leaders would be more able to enjoy these situations, but also be more efficient in choosing appropriate expressions for building constructive dialogue. We suggest, that emotionally intelligent leaders show more positive emotional expressions than low-EI leaders. To study these hypotheses we observed performance review discussions of 40 leaders (24 female) with 78 (45 female) of their followers. Each leader held a discussion with two followers. Psychophysiological methods were chosen because they provide objective and continuous data from the whole duration of the discussions. We recorded sweating of the hands (electrodermal activation) by electrodes placed to the fingers of the non-dominant hand to assess the stress-related physiological arousal of the leaders. In addition, facial electromyography was recorded from cheek (zygomaticus major, activated during e.g. smiling) and periocular (orbicularis oculi, activated during smiling) muscles using electrode pairs placed on the left side of the face. Leader’s trait EI was measured with a 360 questionnaire, filled by each leader’s followers, peers, managers and by themselves. High-EI leaders had less sweating of the hands (p = .007) than the low-EI leaders. It is thus suggested that the high-EI leaders experienced less physiological stress during the discussions. Also, high scores in the factor “Using of emotions” were related to more facial muscle activation indicating positive emotional expressions (cheek muscle: p = .048; periocular muscle: p = .076, almost statistically significant). The results imply that emotionally intelligent managers are positively relaxed during s social leadership situations such as a performance review discussion. The current study also highlights the importance of EI in face-to-face social interaction, given the central role facial expressions have in interaction situations. The study also offers new insight to the biological basis of trait EI. It is suggested that the identification, forming, and intelligently using of facial expressions are skills that could be trained during leadership development courses.

Keywords: emotional intelligence, leadership, performance review discussion, psychophysiology, social interaction

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Authors: Siba Soren, Purnendu Parhi

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Today, the world is facing a severe challenge due to depletion of traditional fossil fuels. Scientists across the globe are working for a solution that involves a dramatic shift to practical and environmentally sustainable energy sources. High-capacity energy systems, such as metal-air batteries, fuel cells, are highly desirable to meet the urgent requirement of sustainable energies. Among the fuel cells, Direct methanol fuel cells (DMFCs) are recognized as an ideal power source for mobile applications and have received considerable attention in recent past. In this advanced electrochemical energy conversion technologies, Oxygen Reduction Reaction (ORR) is of utmost importance. However, the poor kinetics of cathodic ORR in DMFCs significantly hampers their possibilities of commercialization. The oxygen is reduced in alkaline medium either through a 4-electron (equation i) or a 2-electron (equation ii) reduction pathway at the cathode ((i) O₂ + 2H₂O + 4e⁻ → 4OH⁻, (ii) O₂ + H₂O + 2e⁻ → OH⁻ + HO₂⁻ ). Due to sluggish ORR kinetics the ability to control the reduction of molecular oxygen electrocatalytically is still limited. The electrocatalytic ORR starts with adsorption of O₂ on the electrode surface followed by O–O bond activation/cleavage and oxide removal. The reaction further involves transfer of 4 electrons and 4 protons. The sluggish kinetics of ORR, on the one hand, demands high loading of precious metal-containing catalysts (e.g., Pt), which unfavorably increases the cost of these electrochemical energy conversion devices. Therefore, synthesis of active electrocatalyst with an increase in ORR performance is need of the hour. In the recent literature, there are many reports on transition metal oxide (TMO) based ORR catalysts for their high activity TMOs are also having drawbacks like low electrical conductivity, which seriously affects the electron transfer process during ORR. It was found that 2D graphene layer is having high electrical conductivity, large surface area, and excellent chemical stability, appeared to be an ultimate choice as support material to enhance the catalytic performance of bare metal oxide. g-C₃N₄ is also another candidate that has been used by the researcher for improving the ORR performance of metal oxides. This material provides more active reaction sites than other N containing carbon materials. Rare earth oxide like CeO₂ is also a good candidate for studying the ORR activity as the metal oxide not only possess unique electronic properties but also possess catalytically active sites. Here we will discuss the ORR performance (in alkaline medium) of N-rGO/C₃N₄ supported nano Cerium Oxides hybrid synthesized by microwave assisted Solvothermal method. These materials exhibit superior electrochemical stability and methanol tolerance capability to that of commercial Pt/C.

Keywords: oxygen reduction reaction, electrocatalyst, cerium oxide, graphene

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Authors: Maher Z. Mohammed, Barry G. Clarke

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As an alternative to stone column in fine grained soils, it is possible to create stiffened columns of soils using electroosmosis (electroosmotic piles). This program of this research is to establish the effectiveness and efficiency of the process in different soils. The aim of this study is to assess the capability of electroosmosis treatment in a range of composite soils. The combined electroosmotic and preloading equipment developed by Nizar and Clarke (2013) was used with an octagonal array of anodes surrounding a single cathode in a nominal 250mm diameter 300mm deep cylinder of soil and 80mm anode to cathode distance. Copper coiled springs were used as electrodes to allow the soil to consolidate either due to an external vertical applied load or electroosmosis. The equipment was modified to allow the temperature to be monitored during the test. Electroosmotic tests were performed on China Clay Grade E kaolin and calcium bentonite (Bentonex CB) mixed with sand fraction C (BS 1881 part 131) at different ratios by weight; (0, 23, 33, 50 and 67%) subjected to applied voltages (5, 10, 15 and 20). The soil slurry was prepared by mixing the dry soil with water to 1.5 times the liquid limit of the soil mixture. The mineralogical and geotechnical properties of the tested soils were measured before the electroosmosis treatment began. In the electroosmosis cell tests, the settlement, expelled water, variation of electrical current and applied voltage, and the generated heat was monitored during the test time for 24 osmotic tests. Water content was measured at the end of each test. The electroosmotic tests are divided into three phases. In Phase 1, 15 kPa was applied to simulate a working platform and produce a uniform soil which had been deposited as a slurry. 50 kPa was used in Phase 3 to simulate a surcharge load. The electroosmotic treatment was only performed during Phase 2 where a constant voltage was applied through the electrodes in addition to the 15 kPa pressure. This phase was stopped when no further water was expelled from the cell, indicating the electroosmotic process had stopped due to either the degradation of the anode or the flow due to the hydraulic gradient exactly balanced the electroosmotic flow resulting in no flow. Control tests for each soil mixture were carried out to assess the behaviour of the soil samples subjected to only an increase of vertical pressure, which is 15kPa in Phase 1 and 50kPa in Phase 3. Analysis of the experimental results from this study showed a significant dewatering effect on the soil slurries. The water discharged by the electroosmotic treatment process decreased as the sand content increased. Soil temperature increased significantly when electrical power was applied and drops when applied DC power turned off or when the electrode degraded. The highest increase in temperature was found in pure clays at higher applied voltage after about 8 hours of electroosmosis test.

Keywords: electrokinetic treatment, electrical conductivity, electroosmotic consolidation, electroosmosis permeability ratio

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Authors: Gondrexon, Gonon, Mendil-Jakani, Mareau

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Proton Exchange Membrane Fuel Cells (PEMFCs) seems to be a promising device used for converting hydrogen into electricity. PEMFC is made of a Membrane Electrode Assembly (MEA) composed of a Proton Exchange Membrane (PEM) sandwiched by two catalytic layers. Nowadays, specific performances are targeted in order to ensure the long-term expansion of this technology. Current polymers used (perfluorinated as Nafion®) are unsuitable (loss of mechanical properties) for the high-temperature range. To overcome this issue, sulfonated polyaromatic polymers appear to be a good alternative since it has very good thermomechanical properties. However, their proton conductivity and chemical stability (oxidative resistance to H2O2 formed during fuel cell (FC) operating) are very low. In our team, we patented an original concept of hybrid membranes able to fulfill the specific requirements for PEMFC. This idea is based on the improvement of commercialized polymer membrane via an easy and processable stabilization thanks to sol-gel (SG) chemistry with judicious embeded chemical functions. This strategy is thus breaking up with traditional approaches (design of new copolymers, use of inorganic charges/additives). In 2020, we presented the elaboration and functional properties of a 1st generation of hybrid membranes with promising performances and durability. The latter was made by self-condensing a SG phase with 3(mercaptopropyl)trimethoxysilane (MPTMS) inside a commercial sPEEK host membrane. The successful in-situ condensation reactions of the MPTMS was demonstrated by measures of mass uptakes, FTIR spectroscopy (presence of C-Haliphatics) and solid state NMR 29Si (T2 & T3 signals of self-condensation products). The ability of the SG phase to prevent the oxidative degradation of the sPEEK phase (thanks to thiol chemical functions) was then proved with H2O2 accelerating tests and FC operating tests. A 2nd generation made of thiourea functionalized SG precursors (named HTU & TTU) was made after. By analysing in depth the morphologies of these different hybrids by direct space analysis (AFM/SEM/TEM) and reciprocal space analysis (SANS/SAXS/WAXS), we highlighted that both SG phase morphology and its localisation into the host has a huge impact on the PEM functional properties observed. This relationship is also dependent on the chemical function embedded. The hybrids obtained have shown very good chemical resistance during aging test (exposed to H2O2) compared to the commercial sPEEK. But the chemical function used is considered as “sacrificial” and cannot react indefinitely with H2O2. Thus, we are now working on a 3rd generation made of both sacrificial/regenerative chemical functions which are expected to inhibit the chemical aging of sPEEK more efficiently. With this work, we are confident to reach a predictive approach of the key parameters governing the final properties.

Keywords: fuel cells, ionomers, membranes, sPEEK, chemical stability

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Authors: Gerhard Gritsch, Ana Skupch, Manfred Hartmann, Wolfgang Frühwirt, Hannes Perko, Dieter Grossegger, Tilmann Kluge

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Rehabilitation of stroke patients is dominated by classical physiotherapy. Nowadays, a field of research is the application of neurofeedback techniques in order to help stroke patients to get rid of their motor impairments. Especially, if a certain limb is completely paralyzed, neurofeedback is often the last option to cure the patient. Certain exercises, like the imagination of the impaired motor function, have to be performed to stimulate the neuroplasticity of the brain, such that in the neighboring parts of the injured cortex the corresponding activity takes place. During the exercises, it is very important to keep the motivation of the patient at a high level. For this reason, the missing natural feedback due to a movement of the effected limb may be replaced by a synthetic feedback based on the motor-related brain function. To generate such a synthetic feedback a system is needed which measures, detects, localizes and visualizes the motor related µ-rhythm. Fast therapeutic success can only be achieved if the feedback features high specificity, comes in real-time and without large delay. We describe such an approach that offers a 3D visualization of µ-rhythms in real time with a delay of 500ms. This is accomplished by combining smart EEG preprocessing in the frequency domain with source localization techniques. The algorithm first selects the EEG channel featuring the most prominent rhythm in the alpha frequency band from a so-called motor channel set (C4, CZ, C3; CP6, CP4, CP2, CP1, CP3, CP5). If the amplitude in the alpha frequency band of this certain electrode exceeds a threshold, a µ-rhythm is detected. To prevent detection of a mixture of posterior alpha activity and µ-activity, the amplitudes in the alpha band outside the motor channel set are not allowed to be in the same range as the main channel. The EEG signal of the main channel is used as template for calculating the spatial distribution of the µ - rhythm over all electrodes. This spatial distribution is the input for a inverse method which provides the 3D distribution of the µ - activity within the brain which is visualized in 3D as color coded activity map. This approach mitigates the influence of lid artifacts on the localization performance. The first results of several healthy subjects show that the system is capable of detecting and localizing the rarely appearing µ-rhythm. In most cases the results match with findings from visual EEG analysis. Frequent eye-lid artifacts have no influence on the system performance. Furthermore, the system will be able to run in real-time. Due to the design of the frequency transformation the processing delay is 500ms. First results are promising and we plan to extend the test data set to further evaluate the performance of the system. The relevance of the system with respect to the therapy of stroke patients has to be shown in studies with real patients after CE certification of the system. This work was performed within the project ‘LiveSolo’ funded by the Austrian Research Promotion Agency (FFG) (project number: 853263).

Keywords: real-time EEG neuroimaging, neurofeedback, stroke, EEG–signal processing, rehabilitation

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Authors: Chandan Kundu, Sankar Bhattacharya

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A significant disadvantage of fossil fuel energy production is the considerable amount of carbon dioxide (CO₂) released, which is one of the contributors to climate change. Apart from environmental concerns, changing fossil fuel prices have pushed society gradually towards renewable energy sources in recent years. Biomass is a plentiful and renewable resource and a source of carbon. Recent years have seen increased research interest in generating fuels and chemicals from biomass. Unlike fossil-based resources, biomass is composed of lignocellulosic material, which does not contribute to the increase in atmospheric CO₂ over a longer term. These considerations contribute to the current move of the chemical industry from non-renewable feedstock to renewable biomass. This presentation focuses on generating bio-oil and two major platform chemicals that can potentially improve the environment. Thermochemical processes such as pyrolysis are considered viable methods for producing bio-oil and biomass-based platform chemicals. Fluidized bed reactors, on the other hand, are known to boost bio-oil yields during pyrolysis due to their superior mixing and heat transfer features, as well as their scalability. This review and the associated experimental work are focused on the thermochemical conversion of biomass to bio-oil and two high-value platform chemicals, Levoglucosenone (LGO) and 5-Chloromethyl furfural (5-CMF), in a fluidized bed reactor. These two active molecules with distinct features can potentially be useful monomers in the chemical and pharmaceutical industries since they are well adapted to the manufacture of biologically active products. This process took several meticulous steps. To begin, the biomass was delignified using a peracetic acid pretreatment to remove lignin. Because of its complicated structure, biomass must be pretreated to remove the lignin, increasing access to the carbohydrate components and converting them to platform chemicals. The biomass was then characterized by Thermogravimetric analysis, Synchrotron-based THz spectroscopy, and in-situ DRIFTS in the laboratory. Based on the results, a continuous-feeding fluidized bed reactor system was constructed to generate platform chemicals from pretreated biomass using hydrogen chloride acid-gas as a catalyst. The procedure also yields biochar, which has a number of potential applications, including soil remediation, wastewater treatment, electrode production, and energy resource utilization. Consequently, this research also includes a preliminary experimental evaluation of the biochar's prospective applications. The biochar obtained was evaluated for its CO₂ and steam reactivity. The outline of the presentation will comprise the following: Biomass pretreatment for effective delignification Mechanistic study of the thermal and thermochemical conversion of biomass Thermochemical conversion of untreated and pretreated biomass in the presence of an acid catalyst to produce LGO and CMF A thermo-catalytic process for the production of LGO and 5-CMF in a continuously-fed fluidized bed reactor and efficient separation of chemicals Use of biochar generated from the platform chemicals production through gasification

Keywords: biomass, pretreatment, pyrolysis, levoglucosenone

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Authors: Cyril O. Ehi-Eromosele, Ajayi Kayode

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The Li-rich layered metal oxides (LLO) are the most promising candidates for promising electrodes of high energy Li-ion battery (LIB). In literature, these electrode system has either been designed as a hetero-structure of the primary components (composite) or as a core-shell structure with improved electrochemistry reported for both configurations when compared with its primary components. With the on-going efforts to improve on the electrochemical performance of the LIB, it is important to investigate comparatively the structural and electrochemical characteristics of the core-shell like and ‘composite’ forms of these materials with the same compositions and synthesis conditions which could influence future engineering of these materials. Therefore, this study concerns the structural and electrochemical properties of the ‘composite’ and core-shell like LLO cathode materials with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₂O₂ (LiNi₀.₅Mn₀.₃Co₀.₂O₂ as core and Li₂MnO₃ as the shell). The results show that the core-shell sample (–CS) gave better electrochemical performance than the ‘composite’ sample (–C). Both samples gave the same initial charge capacity of ~300 mAh/g when cycled at 10 mA/g and comparable charge capacity (246 mAh/g for the –CS sample and 240 mAh/g for the –C sample) when cycled at 200 mA/g. However, the –CS sample gave a higher initial discharge capacity at both current densities. The discharge capacity of the –CS sample was 232 mAh/g and 164 mAh/g while the –C sample is 208 mAh/g and 143 mAh/g at the current densities of 10 mA/g and 200 mA/g, respectively. Electrochemical impedance spectroscopy (EIS) results show that the –CS sample generally exhibited a smaller resistance than the –C sample both for the uncycled and after 50th cycle. Detailed structural analysis is on-going, but preliminary results show that the –CS sample had bigger unit cell volume and a higher degree of cation mixing. The thermal stability of the –CS sample was higher than the –C sample. XPS investigation also showed that the pristine –C sample gave a more reactive surface (showing formation of carbonate species to a greater degree) which could result in the greater resistance seen in the EIS result. To reinforce the results obtained for the 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₃O₂ composition, the same investigations were extended to another ‘composite’ and core-shell like LLO cathode materials also with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂. In this case, the aim was to determine the electrochemical performance of the material using a low Ni content (LiNi₀.₃Mn₀.₃Co₀.₃O₂) as the core to clarify the contributions of the core-shell configuration to the electrochemical performance of these materials. Ni-rich layered oxides show active catalytic surface leading to electrolyte oxidation resulting in poor thermal stability and cycle life. Here, the core-shell sample also gave better electrochemical performance than the ‘composite’ sample with 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂ composition. Furthermore, superior electrochemical performance was also recorded for the core-shell like spinel modified LLO (0.5Li₂MnO₃-0.45LiNi₀.₅Mn₀.₃Co₀.₂O₂-0.05LiNi₀.₅Mn₁.₅O₄) when compared to the composite system. These results show that the core-shell configuration can generally be used to improve the structural and electrochemical properties of the LLO and spinel modified LLO materials.

Keywords: lithium-ion battery, lithium rich oxide cathode, core-shell structure, composite structure

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Authors: Hongyan Chen, Megan Jobson, Andrew J. Masters, Maria Gonzalez-Miquel, Simon Halstead, Mayri Diaz de Rienzo

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Ionic liquids offer excellent advantages over conventional solvents for industrial extraction of metals from aqueous solutions, where such extraction processes bring opportunities for recovery, reuse, and recycling of valuable resources and more sustainable production pathways. Recent research on the use of ionic liquids for extraction confirms their high selectivity and low volatility, but there is relatively little focus on how their properties can be best exploited in practice. This work addresses gaps in research on process modelling and simulation, to support development, design, and optimisation of these processes, focusing on the separation of the highly similar transition metals, cobalt, and nickel. The study exploits published experimental results, as well as new experimental results, relating to the separation of Co and Ni using trihexyl (tetradecyl) phosphonium chloride. This extraction agent is attractive because it is cheaper, more stable and less toxic than fluorinated hydrophobic ionic liquids. This process modelling work concerns selection and/or development of suitable models for the physical properties, distribution coefficients, for mass transfer phenomena, of the extractor unit and of the multi-stage extraction flowsheet. The distribution coefficient model for cobalt and HCl represents an anion exchange mechanism, supported by the literature and COSMO-RS calculations. Parameters of the distribution coefficient models are estimated by fitting the model to published experimental extraction equilibrium results. The mass transfer model applies Newman’s hard sphere model. Diffusion coefficients in the aqueous phase are obtained from the literature, while diffusion coefficients in the ionic liquid phase are fitted to dynamic experimental results. The mass transfer area is calculated from the surface to mean diameter of liquid droplets of the dispersed phase, estimated from the Weber number inside the extractor. New experiments measure the interfacial tension between the aqueous and ionic phases. The empirical models for predicting the density and viscosity of solutions under different metal loadings are also fitted to new experimental data. The extractor is modelled as a continuous stirred tank reactor with mass transfer between the two phases and perfect phase separation of the outlet flows. A multistage separation flowsheet simulation is set up to replicate a published experiment and compare model predictions with the experimental results. This simulation model is implemented in gPROMS software for dynamic process simulation. The results of single stage and multi-stage flowsheet simulations are shown to be in good agreement with the published experimental results. The estimated diffusion coefficient of cobalt in the ionic liquid phase is in reasonable agreement with published data for the diffusion coefficients of various metals in this ionic liquid. A sensitivity study with this simulation model demonstrates the usefulness of the models for process design. The simulation approach has potential to be extended to account for other metals, acids, and solvents for process development, design, and optimisation of extraction processes applying ionic liquids for metals separations, although a lack of experimental data is currently limiting the accuracy of models within the whole framework. Future work will focus on process development more generally and on extractive separation of rare earths using ionic liquids.

Keywords: distribution coefficient, mass transfer, COSMO-RS, flowsheet simulation, phosphonium

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Authors: Albert Mufundirwa, Satoru Yoshioka, K. Ogi, Takeharu Sugiyama, George F. Harrington, Bretislav Smid, Benjamin Cunning, Kazunari Sasaki, Akari Hayashi, Stephen M. Lyth

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Polymer electrolyte membrane fuel cells (PEMFCs) are electrochemical energy conversion devices used for portable, residential and vehicular applications due to their low emissions, high efficiency, and quick start-up characteristics. However, PEMFCs generally use expensive, Pt-based electrocatalysts as electrode catalysts. Due to the high cost and limited availability of platinum, research and development to either drastically reduce platinum loading, or replace platinum with alternative catalysts is of paramount importance. A combination of high surface area supports and nano-structured active sites is essential for effective operation of catalysts. We synthesize carbon foam supports by thermal decomposition of sodium ethoxide, using a template-free, gram scale, cheap, and scalable pyrolysis method. This carbon foam has a high surface area, highly porous, three-dimensional framework which is ideal for electrochemical applications. These carbon foams can have surface area larger than 2500 m²/g, and electron microscopy reveals that they have micron-scale cells, separated by few-layer graphene-like carbon walls. We applied this carbon foam as a platinum catalyst support, resulting in the improved electrochemical surface area and mass activity for the oxygen reduction reaction (ORR), compared to carbon black. Similarly, silver-decorated carbon foams showed higher activity and efficiency for electrochemical carbon dioxide conversion than silver-decorated carbon black. A promising alternative to Pt-catalysts for the ORR is iron-impregnated nitrogen-doped carbon catalysts (Fe-N-C). Doping carbon with nitrogen alters the chemical structure and modulates the electronic properties, allowing a degree of control over the catalytic properties. We have adapted our synthesis method to produce nitrogen-doped carbon foams with large surface area, using triethanolamine as a nitrogen feedstock, in a novel bottom-up protocol. These foams are then infiltrated with iron acetate (FeAc) and pyrolysed to form Fe-N-C foams. The resulting Fe-N-C foam catalysts have high initial activity (half-wave potential of 0.68 VRHE), comparable to that of commercially available Pt-free catalysts (e.g., NPC-2000, Pajarito Powder) in acid solution. In alkaline solution, the Fe-N-C carbon foam catalysts have a half-wave potential of 0.89 VRHE, which is higher than that of NPC-2000 by almost 10 mVRHE, and far out-performing platinum. However, the durability is still a problem at present. The lessons learned from X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements will be used to carefully design Fe-N-C catalysts for higher performance PEMFCs.

Keywords: carbon-foam, polymer electrolyte membrane fuel cells, platinum, Pt-free, Fe-N-C, ORR

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Authors: Guillaume Soubeyran, Fabrice Micoud, Benoit Morin, Jean-Philippe Poirot-Crouvezier, Magali Reytier

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Proton Exchange Membrane Fuel Cell (PEMFC) technology is considered as a solution for the reduction of CO2 emissions. However, this technology still meets several challenges for high-scale industrialization. In this context, the increase of durability remains a critical aspect for competitiveness of this technology. Fortunately, performance degradations in nominal operating conditions is partially reversible, meaning that if specific conditions are applied, a partial recovery of fuel cell performance can be achieved, while irreversible degradations can only be mitigated. Thus, it is worth studying the optimal conditions to rejuvenate these reversible degradations and assessing the long-term impact of such procedures on the performance of the cell. Reversible degradations consist mainly of anode Pt active sites poisoning by carbon monoxide at the anode, heterogeneities in water management during use, and oxidation/deactivation of Pt active sites at the cathode. The latter is identified as a major source of reversible performance loss caused by the presence oxygen, high temperature and high cathode potential that favor platinum oxidation, especially in high efficiency operating points. Hence, we studied here a recovery procedure aiming at reducing the platinum oxides by decreasing cathode potential during operation. Indeed, the application of short air starvation phase leads to a drop of cathode potential. Cell performances are temporarily increased afterwards. Nevertheless, local temperature and current heterogeneities within the cells are favored and shall be minimized. The consumption of fuel during the recovery phase shall also be considered to evaluate the global efficiency. Consequently, the purpose of this work is to find an optimal compromise between the recovery of reversible degradations by air starvation, the increase of global cell efficiency and the mitigation of irreversible degradations effects. Different operating parameters have first been studied such as cell voltage, temperature and humidity in single cell set-up. Considering the global PEMFC system efficiency, tests showed that reducing duration of recovery phase and reducing cell voltage was the key to ensure an efficient recovery. Recovery phase frequency was a major factor as well. A specific method was established to find the optimal frequency depending on the duration and voltage of the recovery phase. Then, long-term degradations have also been studied by applying FC-DLC cycles based on NEDC cycles on a 4-cell short stack by alternating test sequences with and without recovery phases. Depending on recovery phase timing, cell efficiency during the cycle was increased up to 2% thanks to a mean voltage increase of 10 mV during test sequences with recovery phases. However, cyclic voltammetry tests results suggest that the implementation of recovery phases causes an acceleration of the decrease of platinum active areas that could be due to the high potential variations applied to the cathode electrode during operation.

Keywords: durability, PEMFC, recovery procedure, reversible degradation

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Authors: Keivan Davami, Michael Munther, Lloyd Hackel

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The control of properties and material behavior by implementing thermal-mechanical processes is based on mechanical deformation and annealing according to a precise schedule that will produce a unique and stable combination of grain structure, dislocation substructure, texture, and dispersion of precipitated phases. The authors recently developed a thermal-mechanical technique to stabilize the microstructure of additively manufactured nickel-based superalloys even after exposure to high temperatures. However, the mechanism(s) that controls this stability is still under investigation. Laser peening (LP), also called laser shock peening (LSP), is a shock based (50 ns duration) post-processing technique used for extending performance levels and improving service life of critical components by developing deep levels of plastic deformation, thereby generating high density of dislocations and inducing compressive residual stresses in the surface and deep subsurface of components. These compressive residual stresses are usually accompanied with an increase in hardness and enhance the material’s resistance to surface-related failures such as creep, fatigue, contact damage, and stress corrosion cracking. While the LP process enhances the life span and durability of the material, the induced compressive residual stresses relax at high temperatures (>0.5Tm, where Tm is the absolute melting temperature), limiting the applicability of the technology. At temperatures above 0.5Tm, the compressive residual stresses relax, and yield strength begins to drop dramatically. The principal reason is the increasing rate of solid-state diffusion, which affects both the dislocations and the microstructural barriers. Dislocation configurations commonly recover by mechanisms such as climbing and recombining rapidly at high temperatures. Furthermore, precipitates coarsen, and grains grow; virtually all of the available microstructural barriers become ineffective.Our results indicate that by using “cyclic” treatments with sequential LP and annealing steps, the compressive stresses survive, and the microstructure is stable after exposure to temperatures exceeding 0.5Tm for a long period of time. When the laser peening process is combined with annealing, dislocations formed as a result of LPand precipitates formed during annealing have a complex interaction that provides further stability at high temperatures. From a scientific point of view, this research lays the groundwork for studying a variety of physical, materials science, and mechanical engineering concepts. This research could lead to metals operating at higher sustained temperatures enabling improved system efficiencies. The strengthening of metals by a variety of means (alloying, work hardening, and other processes) has been of interest for a wide range of applications. However, the mechanistic understanding of the often complex processes of interactionsbetween dislocations with solute atoms and with precipitates during plastic deformation have largely remained scattered in the literature. In this research, the elucidation of the actual mechanisms involved in the novel cyclic LP/annealing processes as a scientific pursuit is investigated through parallel studies of dislocation theory and the implementation of advanced experimental tools. The results of this research help with the validation of a novel laser processing technique for high temperature applications. This will greatly expand the applications of the laser peening technology originally devised only for temperatures lower than half of the melting temperature.

Keywords: laser shock peening, mechanical properties, indentation, high temperature stability

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Authors: S. A. Krutovertsev, A. E. Tarasova, L. S. Krutovertseva, O. M. Ivanova

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The aim of the work was to get stable sensitive films with good sensitivity to ethanolamine (C2H7NO) in air. Ethanolamine is used as adsorbent in different processes of gas purification and separation. Besides it has wide industrial application. Chemical sensors of sorption type are widely used for gas analysis. Their behavior is determined by sensor characteristics of sensitive sorption layer. Forming conditions and characteristics of chemical gas sensors based on nanostructured modified silica films activated by different admixtures have been studied. As additives molybdenum containing polyoxometalates of the eighteen series were incorporated in silica films. The method of hydrolythic polycondensation from tetraethyl orthosilicate solutions was used for forming such films in this work. The method’s advantage is a possibility to introduce active additives directly into an initial solution. This method enables to obtain sensitive thin films with high specific surface at room temperature. Particular properties make polyoxometalates attractive as active additives for forming of gas-sensitive films. As catalyst of different redox processes, they can either accelerate the reaction of the matrix with analyzed gas or interact with it, and it results in changes of matrix’s electrical properties Polyoxometalates based films were deposited on the test structures manufactured by microelectronic planar technology with interdigitated electrodes. Modified silica films were deposited by a casting method from solutions based on tetraethyl orthosilicate and polyoxometalates. Polyoxometalates were directly incorporated into initial solutions. Composite nanostructured films were deposited by drop casting method on test structures with a pair of interdigital metal electrodes formed at their surface. The sensor’s active area was 4.0 x 4.0 mm, and electrode gap was egual 0.08 mm. Morphology of the layers surface were studied with Solver-P47 scanning probe microscope (NT-MDT, Russia), the infrared spectra were investigated by a Bruker EQUINOX 55 (Germany). The conditions of film formation varied during the tests. Electrical parameters of the sensors were measured electronically in real-time mode. Films had highly developed surface with value of 450 m2/g and nanoscale pores. Thickness of them was 0,2-0,3 µm. The study shows that the conditions of the environment affect markedly the sensors characteristics, which can be improved by choosing of the right procedure of forming and processing. Addition of polyoxometalate into silica film resulted in stabilization of film mass and changed markedly of electrophysical characteristics. Availability of Mn3P2Mo18O62 into silica film resulted in good sensitivity and selectivity to ethanolamine. Sensitivity maximum was observed at weight content of doping additive in range of 30–50% in matrix. With ethanolamine concentration changing from 0 to 100 ppm films’ conductivity increased by 10-12 times. The increase of sensor’s sensitivity was received owing to complexing reaction of tested substance with cationic part of polyoxometalate. This fact results in intramolecular redox reaction which sharply change electrophysical properties of polyoxometalate. This process is reversible and takes place at room temperature.

Keywords: ethanolamine, gas analysis, polyoxometalate, silica film

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