Search results for: electrochemical method

Authors: Sori Won, Bosung Seo, Kwangsuk Park, Seok Hong Min, Tae Kwon Ha

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With the increased needs for lightweight materials in automobile industry, the usage of aluminum alloys becomes prevailed as components and car bodies due to their comparative specific strength. These parts composed of different aluminum alloys should be connected each other, where welding technologies are commonly applied. Among various welding methods, friction welding method as a solid state welding gets to be popular in joining aluminum alloys as it does not produce a defect such as blowhole that is often formed during typical welding processes. Once two metals are joined, corrosion would become an issue due to different electrochemical potentials. In this study, we investigated variations of corrosion properties when Duralumin and AA6063 were joined by friction welding. From the polarization test, it was found that the potential of the welded was placed between those of two original metals, which could be explained by a concept of mixed potential. Pitting is a common form as a result of the corrosion of aluminum alloys when they are exposed to 3.5 wt% NaCl solution. However, when two different aluminum alloys (Duralumin and AA6063) were joined, pitting corrosion occurred severely and uniformly in Duralumin while there were a few pits around precipitates in AA6063, indicating that AA6063 was cathodically protected.

Keywords: corrosion properties, friction welding, dissimilar Al alloys, polarization test

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Authors: M. K. Balyan

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The main principles of X-ray Fourier interferometric holography method are discussed. The object image is reconstructed by the mathematical method of Fourier transformation. The three methods are presented – method of approximation, iteration method and step by step method. As an example the complex amplitude transmission coefficient reconstruction of a beryllium wire is considered. The results reconstructed by three presented methods are compared. The best results are obtained by means of step by step method.

Keywords: dynamical diffraction, hologram, object image, X-ray holography

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Authors: N. Guruprasad

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This paper presents a modification of approximation method for transportation problems. The initial basic feasible solution can be computed using either Russel's or Vogel's approximation methods. Russell’s approximation method provides another excellent criterion that is still quick to implement on a computer (not manually) In most cases Russel's method yields a better initial solution, though it takes longer than Vogel's method (finding the next entering variable in Russel's method is in O(n1*n2), and in O(n1+n2) for Vogel's method). However, Russel's method normally has a lesser total running time because less pivots are required to reach the optimum for all but small problem sizes (n1+n2=~20). With this motivation behind we have incorporated a variation of the same – what we have proposed it has TMC (Total Modified Cost) to obtain fast and efficient solutions.

Keywords: computation, efficiency, modified cost, Russell’s approximation method, transportation, Vogel’s approximation method

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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: Bib Paruhum Silalahi, Djihad Wungguli, Sugi Guritman

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Steepest descent method is a simple gradient method for optimization. This method has a slow convergence in heading to the optimal solution, which occurs because of the zigzag form of the steps. Barzilai and Borwein modified this algorithm so that it performs well for problems with large dimensions. Barzilai and Borwein method results have sparked a lot of research on the method of steepest descent, including alternate minimization gradient method and Yuan method. Inspired by previous works, we modified the step size of the steepest descent method. We then compare the modification results against the Barzilai and Borwein method, alternate minimization gradient method and Yuan method for quadratic function cases in terms of the iterations number and the running time. The average results indicate that the steepest descent method with the new step sizes provide good results for small dimensions and able to compete with the results of Barzilai and Borwein method and the alternate minimization gradient method for large dimensions. The new step sizes have faster convergence compared to the other methods, especially for cases with large dimensions.

Keywords: steepest descent, line search, iteration, running time, unconstrained optimization, convergence

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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: Peter M. Schneider, Batyr Garlyyev, Sebastian A. Watzele, Aliaksandr S. Bandarenka

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Functional nanostructures such as nanoparticles are a promising class of materials for energy applications due to their unique properties. Bottom-up synthetic routes for nanostructured materials often involve multiple synthesis steps and the use of surfactants, reducing agents, or stabilizers. This results in complex and extensive synthesis protocols. In recent years, a novel top-down synthesis approach to form metal nanoparticles has been established, in which bulk metal wires are immersed in an electrolyte (primarily alkali earth metal based) and subsequently subjected to a high alternating potential. This leads to the generation of nanoparticles dispersed in the electrolyte. The main advantage of this facile top-down approach is that there are no reducing agents, surfactants, or precursor solutions. The complete synthesis can be performed in one pot involving one main step with consequent washing and drying of the nanoparticles. More recent studies investigated the effect of synthesis parameters such as potential amplitude, frequency, electrolyte composition, and concentration on the size and shape of the nanoparticles. Here, we investigate the electrochemical erosion of various metal wires such as Ti, Pt, Pd, and Sn in various electrolyte compositions via this facile top-down technique and its experimental optimization to successfully synthesize nanostructured materials for various energy applications. As an example, for Pt and Pd, homogeneously distributed nanoparticles on carbon support can be obtained. These materials can be used as electrocatalyst materials for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER), respectively. In comparison, the top-down erosion of Sn wires leads to the formation of nanoparticles, which have great potential as oxygen evolution reaction (OER) support materials. The application of the technique on Ti wires surprisingly leads to the formation of nanowires, which show a high surface area and demonstrate great potential as an alternative support material to carbon.

Keywords: ORR, electrochemistry, electrocatalyst, synthesis

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Authors: Jaejin Han, Jinsub Choi

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Vanadium redox flow battery (VRFB) is a type of redox flow battery which uses vanadium ionic solution as electrolyte. Inside the VRFB, 2.5mm thickness of graphite is generally used as bipolar plate for anti-corrosion of current collector. In this research, thick graphite bipolar plate was substituted by 0.126mm thickness of dimensionally stable anode which was coated with IrO2 on an anodic nanotubular TiO2 substrate. It can provide dimensional advantage over the conventional graphite when the VRFB is used as multi-stack. Ir was coated by using spray coating method in order to enhance electric conductivity. In this study, various electrochemical characterizations were carried out. Cyclic voltammetry data showed activation of Ir in the positive electrode of VRFB. In addition, polarization measurements showed Ir-coated DSA had low overpotential in the positive electrode of VRFB. In cell test results, the DSA-used VRFB showed better efficiency than graphite-used VRFB in voltage and overall efficiency.

Keywords: bipolar plate, DSA (dimensionally stable anode), iridium oxide coating, TiO2 nanotubes, VRFB (vanadium redox flow battery)

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Authors: Concetta Busacca, Leone Frusteri, Orazio Di Blasi, Alessandra Di Blasi

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The large-scale extension of renewable energy led, recently, to the development of efficient and low-cost electrochemical energy storage (EES) systems such as batteries. Although lithium-ion battery (LIB) technology is relatively mature, several issues regarding safety, cyclability, and high costs must be overcome. Thanks to the availability and low cost of sodium, sodium-ion batteries (NIB) have the potential to meet the energy storage needs of the large-scale grid, becoming a valid alternative to LIB in some energy sectors, such as the stationary one. However, important challenges such as low specific energy and short cyclic life due to the large radius of Na+ must be faced to introduce this technology into the market. As an important component of SIBs, cathode materials have a significant effect on the electrochemical performance of SIBs. Recently, sodium layer transition metal oxides, phosphates, and organic compounds have been investigated as cathode materials for SIBs. In particular, phosphate-based compounds such as NaₓMPO₄ (M= Fe, Co, Mn) have been extensively studied as cathodic polyanion materials due to their long cycle stability and appropriate operating voltage. Among these, an interesting cathode material is the NaMnPO₄ based one, thanks to the stability and the high redox potential of the Mn²⁺/Mn³⁺ ion pair (3÷4 V vs. Na+/Na), which allows reaching a high energy density. This work concerns with the synthesis of a composite material based on NaMnPO₄ and carbon nanofibers (NaMnPO₄-CNF) characterized by a mixed crystalline structure between the maricite and olivine phases and a self-standing manufacture obtained by electrospinning technique. The material was tested in a Na-ion battery coin cell in half cell configuration, and showed outstanding electrocatalytic performances with a specific discharge capacity of 125 mAhg⁻¹ and 101 mAhg⁻¹ at 0.3C and 0.6C, respectively, and a retention capacity of about 80% a 0.6C after 100 cycles.

Keywords: electrospinning, self standing materials, Na ion battery, cathode materials

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Authors: Jahangir Ahmad Rather, Emad A. Khudaish, Ahsanulhaq Qurashi, Palanisamy Kannan

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Chemical modification and assembling of fullerenes are fundamentally important for the application of fullerenes as functional molecules and in molecular devices and organic electronic devices. We have synthesized fullerene nanorods C60NRs conjugate via liquid-liquid interface and the synthesized C60NRs was characterized by FTIR spectroscopy, field emission electron microscopy (FESEM) and X-ray diffraction techniques. The C60NRs were immobilized on glassy carbon electrode via surface bound diazonium salts as an impact strategy. This method involves electrografting of p–nitrophenyl to give GCE–Ph–NO2 and then the terminal nitro-group was chemically reduced to GCE–Ph–NH2 in a presence of sodium borohydride/gold–polyaniline nanocomposite (NaBH4/Au–PANI). The Au–PANI composite was synthesized and characterized by FTIR, UV-vis, SEM and EDX techniques. The C60NRs were immobilized on GCE–Ph–NH2 via amination reaction which involves N-H addition across a π-bond on [60] fullerene. The immobilized C60NRs/GCE was subjected to electrochemical reduction in 1.0 M KOH to yield ERC60NRs/GCE sensor. The developed sensor shows high electrocatalytic activity for the detection of ethylparaben (EP) over a concentration range from 0.01 to 0.52 µM with a detection limit (LOD) 3.8 nM. The amount of EP present in the nourishing repair cream (OlAY®) was determined by standard addition method at the developed ERC60NRs/GCE sensor. The total concentration of EP was found to be 0.011 µM (0.1%) and is within the permissible limit of 0.19 % EP in cosmetics according to the European scientific committee (SCCS) on consumer safety on 22 March 2011 (SCCS/1348/11).

Keywords: diazonium salt reduction, ethylparaben (EP), endocrine disruptor, fullerene nanorods (C60NRs), gold–polyaniline nanocomposite (Au–PANI)

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Authors: Fernanda A. Vechietti, Natália O. B. Muniz, Laura C. Treccani, Kurosch. Rezwan, Luis Alberto dos Santos

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CoCr alloys are widely used in prosthetic implants due to their excellent mechanical properties, such as good tensile strength, elastic modulus and wear resistance. Their biocompatibility and lack of corrosion are also prominent features of this alloy. One of the most effective and simple ways to protect metal’s surfaces are treatments, such as electrochemical oxidation by passivation, which is used as a protect release of metallic ions. Another useful treatment is the electropolishing, which is used to reduce the carbide concentration and protrusion at the implanted surface. Electropolishing is a cheap and effective method for treatment of implants, which generally has complex geometries. The purpose of this study is surface modification of the alloy CoCr(ASTM F90-09) by different methods: polishing, electro polishing, passivation and heat treatment for application as biomaterials. The modification of the surface was studied and characterized by SEM, profilometry, wettability and compared to the surface of the samples untreated. The heat treatment and of passivation increased roughness (0.477 µm and 0.825 µm) the samples in relation the sample electropolished and polished(0.131 µm and 0.274 µm) and were observed the improve wettability’s with the increase the roughness.

Keywords: biomaterial, CoCr, surface treatment, heat treatment, roughness

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Authors: Catalina Iticescu, Lucian Georgescu, Mihaela Timofti, Dumitru Dima, Gabriel Murariu

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The amounts of sludge resulting from the treatment of domestic and industrial wastewater can create serious environmental problems if no solutions are found to eliminate them. At present, the predominant method of sewage sludge disposal is to store and use them in agricultural applications. The sewage sludge has fertilizer properties and can be used to enrich agricultural soils due to the nutrient content. In addition to plant growth (nitrogen and phosphorus), the sludge also contains heavy metals in varying amounts. An increasingly used method is the incineration of sludge. Thermal processes can be used to convert large amounts of sludge into useful energy. The sewage sludge analyzed for the present paper was extracted from the Wastewater Treatment Station (WWTP) Galati, Romania. The physico-chemical parameters determined were: pH (upH), nutrients and heavy metals. The determination methods were electrochemical, spectrophotometric and energy dispersive X–ray analyses (EDX). The results of the tests made on the content of nutrients in the sewage sludge have shown that existing nutrients can be used to increase the fertility of agricultural soils. The conclusion reached was that these sludge can be safely used on agricultural land and with good agricultural productivity results. To be able to use sewage sludge as a fuel, we need to know its calorific values. For wet sludge, the caloric power is low, while for dry sludge it is high. Higher calorific value and lower calorific value are determined only for dry solids. The apparatus used to determine the calorific power was a Parr 6755 Solution Calorimeter Calorimeter (Parr Instrument Company USA 2010 model). The calorific capacities for the studied sludge indicate that they can be used successfully in incinerators. Mixed with coal, they can also be used to produce electricity. The advantages are: it reduces the cost of obtaining electricity and considerably reduces the amount of sewage sludge.

Keywords: agriculture, incinerators, properties, sewage sludge

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Authors: Dina Ibrahim Abouelamaiem, Ana Jorge Sobrido, Magdalena Titirici, Paul R. Shearing, Daniel J. L. Brett

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Global warming and scarcity of fossil fuels have had a radical impact on the world economy and ecosystem. The urgent need for alternative energy sources has hence elicited an extensive research for exploiting efficient and sustainable means of energy conversion and storage. Among various electrochemical systems, supercapacitors attracted significant attention in the last decade due to their high power supply, long cycle life compared to batteries and simple mechanism. Recently, the performance of these devices has drastically improved, as tuning of nanomaterials provided efficient charge and storage mechanisms. Carbon materials, in various forms, are believed to pioneer the next generation of supercapacitors due to their attractive properties that include high electronic conductivities, high surface areas and easy processing and functionalization. Cellulose has eco-friendly attributes that are feasible to replace man-made fibers. The carbonization of cellulose yields carbons, including activated carbon and graphite fibers. Activated carbons successively are the most exploited candidates for supercapacitor electrode materials that can be complemented with pseudocapacitive materials to achieve high energy and power densities. In this work, the optimum functionalization conditions of cellulose have been investigated for supercapacitor electrode materials. The precursor was treated with potassium hydroxide (KOH) at different KOH/cellulose ratios prior to the carbonization process in an inert nitrogen atmosphere at 850 °C. The chalky products were washed, dried and characterized with different techniques including transmission electron microscopy (TEM), x-ray tomography and nitrogen adsorption-desorption isotherms. The morphological characteristics and their effect on the electrochemical performances were investigated in two and three-electrode systems. The KOH/cellulose ratios of 0.5:1 and 1:1 exhibited the highest performances with their unique hierarchal porous network structure, high surface areas and low cell resistances. Both samples acquired the best results in three-electrode systems and coin cells with specific gravimetric capacitances as high as 187 F g-1 and 20 F g-1 at a current density of 1 A g-1 and retention rates of 72% and 70%, respectively. This is attributed to the morphology of the samples that constituted of a well-balanced micro-, meso- and macro-porosity network structure. This study reveals that the electrochemical performance doesn’t solely depend on high surface areas but also an optimum pore size distribution, specifically at low current densities. The micro- and meso-pore contribution to the final pore structure was found to dominate at low KOH loadings, reaching ‘equilibrium’ with macropores at the optimum KOH loading, after which macropores dictate the porous network. The wide range of pore sizes is detrimental for the mobility and penetration of electrolyte ions in the porous structures. These findings highlight the influence of various morphological factors on the double-layer capacitances and high performance rates. In addition, they open a platform for the investigation of the optimized conditions for double-layer capacitance that can be coupled with pseudocapacitive materials to yield higher energy densities and capacities.

Keywords: carbon, electrochemical performance, electrodes, KOH/cellulose optimized ratio, morphology, supercapacitor

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Authors: Ahmed Chetouani

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Corrosion is a natural occurring process where it can be defined as the deterioration of materials properties due to its interaction with its environment. Corrosion can lead to failures in plant infrastructure and machines which are usually costly to repair. In terms of loss of contaminated products which will cause environmental damage and possibly costly in terms of human health. The driving force that causes metals to corrode is due to the natural consequence of their temporary existence in metallic form. There is a growing trend in utilizing plant extracts and pharmaceutical compounds as corrosion inhibitors. Exquisite identification of the essential oil of aerial parts of Pelargonium was obtained using hydrodistillation and identification using GC (gas chromatography) and GC/MS (gas chromatography-mass spectrometry). The oil was predominated by Citronellol (22.8%). The inhibitory effect of essential oil and extract of Pelargonium was estimated on the corrosion of mild steel in 1M hydrochloric acid (HCl) using weight loss, Electrochemical Impedance Spectroscopy (EIS) and Tafel polarization curves. Inhibition was found to increase with increasing concentration of the essential oil and extract of Pelargonium. The effect of temperature on the corrosion behaviour of mild steel in 1M HCl with addition of essential oil and extract was also studied and the thermodynamic parameters were determined and discussed. Values of inhibition efficiency were calculated from weight loss, Tafel polarization curves, and EIS. All results are in good agreement. Polarization curves showed that essential oil and extract of Pelargonium behave as mixed type inhibitors in hydrochloric acid. The results obtained showed that the essential oil and extract of Pelargonium could serve as an effective inhibitor of the corrosion of mild steel in Hydrochloric acid solution. To avoid any surprise of toxicity, the majority compounds have been studied by using POM analyses.

Keywords: corrosion inhibition, mild steel, pelargonium oil, extract, electrochemical system, hydrodistillation, side effects, POM Analyses

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Authors: S. Shahrooi, A. Talavari

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Numeral study on the crack and discontinuity using element-free methods has been widely spread in recent years. In this study, for stress intensity factor calculation of the cracked axis under torsional loading has been used from a new element-free method as MLPG method. Region range is discretized by some dispersed nodal points. From method of moving least square (MLS) utilized to create the functions using these nodal points. Then, results of meshless method and finite element method (FEM) were compared. The results is shown which the element-free method was of good accuracy.

Keywords: stress intensity factor, crack, torsional loading, meshless method

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Authors: Abu Hashan Md Mashud, M. Sharif Uddin, Aminur Rahman Khan

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In this paper, we formulate a new problem as a linear programming and Integer Programming problem and maximize profit within the limited budget and limited resources based on the construction of a tea garden problem. It describes a new idea about how to optimize profit and focuses on the practical aspects of modeling and the challenges of providing a solution to a complex real life problem. Finally, a comparative study is carried out among Graphical method, Simplex method and Branch and bound method.

Keywords: integer programming, tea garden, graphical method, simplex method, branch and bound method

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Authors: A. Merzouki, N. Haddaoui

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Polymers have a large reputation as electric insulators. These materials are characterized by weak weight, reduced price and a large domain of physical and chemical properties. They conquered new application domains that were until a recent past the exclusivity of metals. In this work, we used some composite materials (polymers/conductive fillers), as electrodes and we try to cover them with metallic lead layers in order to use them as courant collector grids in lead-acid battery plates.

Keywords: electrodeposition, polymer composites, carbon black, acetylene black

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Authors: Vishakha Kaim, Mookan Natarajan, Sandeep Kaur-Ghumaan

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Hydrogen is one of the most abundant elements present on earth’s crust and considered to be the simplest element in existence. It is not found naturally as a gas on earth and thus has to be manufactured. Hydrogen can be produced from a variety of sources, i.e., water, fossil fuels, or biomass and it is a byproduct of many chemical processes. It is also considered as a secondary source of energy commonly referred to as an energy carrier. Though hydrogen is not widely used as a fuel, it still has the potential for greater use in the future as a clean and renewable source of energy. Electrocatalysis is one of the important source for the production of hydrogen which could contribute to this prominent challenge. Metals such as platinum and palladium are considered efficient for hydrogen production but with limited applications. As a result, a wide variety of metal complexes with earth abundant elements and varied ligand environments have been explored for the electrochemical production of hydrogen. In nature, [FeFe] hydrogenase enzyme present in DesulfoVibrio desulfuricans and Clostridium pasteurianum catalyses the reversible interconversion of protons and electrons into dihydrogen. Since the first structure for the enzyme was reported in 1990s, a range of iron complexes has been synthesized as structural and functional mimics of the enzyme active site. Mn is one of the most desirable element for sustainable catalytic transformations, immediately behind Fe and Ti. Only limited number manganese complexes have been reported in the last two decades as catalysts for proton reduction. Furthermore, redox reactions could be carried out in a facile manner, due to the capability of manganese complexes to be stable at different oxidation states. Herein are reported, four µ2-thiolate bridged manganese complexes [Mn₂(CO)₆(μ-S₂N₄C₁₄H₁₀)] 1, [Mn₂(CO)7(μ- S₂N₄C₁₄H₁₀)] 2, Mn₂(CO)₆(μ-S₄N₂C₁₄H₁₀)] 3 and [Mn₂(CO)(μ- S₄N₂C₁₄H₁₀)] 4 have been synthesized and characterized. The cyclic voltammograms of the complexes displayed irreversible reduction peaks in the range - 0.9 to -1.3 V (vs. Fc⁺/Fc in acetonitrile at 0.1 Vs⁻¹). The complexes were catalytically active towards proton reduction in the presence of trifluoroacetic acid as seen from electrochemical investigations.

Keywords: earth abundant, electrocatalytic, hydrogen, manganese

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Authors: Julieta Daniela Chelaru, Maria Gorea

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The massive demolition of old buildings in recent years has generated tons of waste, especially brick waste. Thus, a concern of recent research is the use of this waste for the production of environmentally friendly concrete. At the same time, corrosion in classical concrete is a current problem. In this context, in the present paper a study was carried out on the corrosion of metal reinforcement in cement mortars with brick waste. The corrosion process was analyzed on four compositions of mortars without and with 15 %, 25 % and 35 % bricks waste replacing the sand. The brick waste has a majority content in SiO2, Al₂O₃, FeO₃ and CaO. The grain size distribution of brick waste was close to that of the sand (dₘₐₓ = 3 mm). The preparation method of the samples was similar to ordinary mortars. The corrosion properties of concrete, at different waste bricks concentrations, on rebar, were investigated by electrochemical measurements (Tafel curves and EIS) at 1 and 6 months. The results obtained at 6 months revealed that the addition of the bricks waste in mortar are improved the anticorrosion properties, in the case of all samples compared with the sample with 0% bricks waste. The best results were obtained in the case of the sample with 15% bricks waste (the efficiency was ≈ 90 %). The corrosion intermediary layer formed on the rebar surface was determined by SEM-EDX.

Keywords: EIS, steel corrosion, steel reinforced concrete, waste materials

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Authors: Camille Perréard, Yoann Ladner, Fanny D'Orlyé, Stéphanie Descroix, Vélan Taniga, Anne Varenne, Cédric Guyon, Michael. Tatoulian, Frédéric Kanoufi, Cyrine Slim, Sophie Griveau, Fethi Bedioui

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The development of micro total analysis systems is of major interest for contaminant and biomarker analysis. As a lab-on-chip integrates all steps of an analysis procedure in a single device, analysis can be performed in an automated format with reduced time and cost, while maintaining performances comparable to those of conventional chromatographic systems. Moreover, these miniaturized systems are either compatible with field work or glovebox manipulations. This work is aimed at developing an analytical microsystem for trace and ultra trace quantitation in complex matrices. The strategy consists in the integration of a sample pretreatment step within the lab-on-chip by a confinement zone where selective ligands are immobilized for target extraction and preconcentration. Aptamers were chosen as selective ligands, because of their high affinity for all types of targets (from small ions to viruses and cells) and their ease of synthesis and functionalization. This integrated target extraction and concentration step will be followed in the microdevice by an electrokinetic separation step and an on-line detection. Polymers consisting of cyclic olefin copolymer (COC) or fluoropolymer (Dyneon THV) were selected as they are easy to mold, transparent in UV-visible and have high resistance towards solvents and extreme pH conditions. However, because of their low chemical reactivity, surface treatments are necessary. For the design of this miniaturized diagnostics, we aimed at modifying the microfluidic system at two scales : (1) on the entire surface of the microsystem to control the surface hydrophobicity (so as to avoid any sample wall adsorption) and the fluid flows during electrokinetic separation, or (2) locally so as to immobilize selective ligands (aptamers) on restricted areas for target extraction and preconcentration. We developed different novel strategies for the surface functionalization of COC and Dyneon, based on plasma, chemical and /or electrochemical approaches. In a first approach, a plasma-induced immobilization of brominated derivatives was performed on the entire surface. Further substitution of the bromine by an azide functional group led to covalent immobilization of ligands through “click” chemistry reaction between azides and terminal alkynes. COC and Dyneon materials were characterized at each step of the surface functionalization procedure by various complementary techniques to evaluate the quality and homogeneity of the functionalization (contact angle, XPS, ATR). With the objective of local (micrometric scale) aptamer immobilization, we developed an original electrochemical strategy on engraved Dyneon THV microchannel. Through local electrochemical carbonization followed by adsorption of azide-bearing diazonium moieties and covalent linkage of alkyne-bearing aptamers through click chemistry reaction, typical dimensions of immobilization zones reached the 50 µm range. Other functionalization strategies, such as sol-gel encapsulation of aptamers, are currently investigated and may also be suitable for the development of the analytical microdevice. The development of these functionalization strategies is the first crucial step in the design of the entire microdevice. These strategies allow the grafting of a large number of molecules for the development of new analytical tools in various domains like environment or healthcare.

Keywords: alkyne-azide click chemistry (CuAAC), electrochemical modification, microsystem, plasma bromination, surface functionalization, thermoplastic polymers

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Authors: Marzieh Joda, Narges Fallah, Neda Afsham

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Graphite-supported two different of morphology α and β -Ni (OH)₂ electrodes were prepared by electrochemical deposition at appropriate potentials with regard to Ni (II)/Ni (III) redox couple under alkaline and acidic conditions, respectively, for selective oxidation of ammonia to nitrogen in the direct electro-oxidation process. Cyclic voltammetry (CV) of the electrolyte containing NH₃ indicated mediation of electron transfer by Ni (OH)₂ and the electrode surface was analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectrometer (RS), and X-ray photoelectron spectroscopy (XPS). Results of surface characterization indicated the presence of α polymorphs which is the stable phase of Ni (OH)₂ /Graphite. Cyclic voltammograms gave information on the nature of electron transfer between nitrogen species and working electrode and revealed that the potential has depended on both nature ammonia oxidation and that of concentration. The mechanism of selective ammonia conversion to nitrogen and byproducts, namely NO₂- and NO₃- was established by Cyclic voltammograms and current efficiency. The removal efficiency and selective conversion of ammonia (0.1 M KNO₃ + 0.01 M Ni(NO₃)₂, pH 11, 250°C) on Nickel Oxide-hydroxide /Graphite was determined based on potential controlled experiments.

Keywords: Electro deposition, Nickel oxide-hydroxide, Nitrogen selectivity, Ammonia oxidation

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Authors: Mohammed Panthakkal Abdul Muthalif, Shanmugasundaram Kanagaraj, Jumi Park, Hangyu Park, Youngson Choe

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The present study reports the incorporation of calcium ions into the CuS counter electrodes (CEs) in order to modify the photovoltaic performance of quantum dot-sensitized solar cells (QDSSCs). Metal ion-doped CuS thin film was prepared by the chemical bath deposition (CBD) method on FTO substrate and used directly as counter electrodes for TiO₂/CdS/CdSe/ZnS photoanodes based QDSSCs. For the Ca-doped CuS thin films, copper nitrate and thioacetamide were used as anionic and cationic precursors. Calcium nitrate tetrahydrate was used as doping material. The surface morphology of Ca-doped CuS CEs indicates that the fragments are uniformly distributed, and the structure is densely packed with high crystallinity. The changes observed in the diffraction patterns suggest that Ca dopant can introduce increased disorder into CuS material structure. EDX analysis was employed to determine the elemental identification, and the results confirmed the presence of Cu, S, and Ca on the FTO glass substrate. The photovoltaic current density – voltage characteristics of Ca-doped CuS CEs shows the specific improvements in open circuit voltage decay (Voc) and short-circuit current density (Jsc). Electrochemical impedance spectroscopy results display that Ca-doped CuS CEs have greater electrocatalytic activity and charge transport capacity than bare CuS. All the experimental results indicate that 20% Ca-doped CuS CE based QDSSCs exhibit high power conversion efficiency (η) of 4.92%, short circuit current density of 15.47 mA cm⁻², open circuit photovoltage of 0.611 V, and fill factor (FF) of 0.521 under illumination of one sun.

Keywords: Ca-doped CuS counter electrodes, surface morphology, chemical bath deposition method, electrocatalytic activity

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Authors: Amir Shafiee Kisomi, Mehrdad Mofidi

Abstract:

Nowadays, fuel cells as a promising alternative for power source have been widely studied owing to their security, high energy density, low operation temperatures, renewable capability and low environmental pollutant emission. The nanoparticles of core-shell type could be widely described in a combination of a shell (outer layer material) and a core (inner material), and their characteristics are greatly conditional on dimensions and composition of the core and shell. In addition, the change in the constituting materials or the ratio of core to the shell can create their special noble characteristics. In this study, a fast technique for the fabrication of a Pd-Co/G/GCE modified electrode is offered. Thermal decomposition reaction of cobalt (II) formate salt over the surface of graphene/glassy carbon electrode (G/GCE) is utilized for the synthesis of Co nanoparticles. The nanoparticles of Pd-Co decorated on the graphene are created based on the following method: (1) Thermal decomposition reaction of cobalt (II) formate salt and (2) the galvanic replacement process Co by Pd2+. The physical and electrochemical performances of the as-prepared Pd-Co/G electrocatalyst are studied by Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive X-ray Spectroscopy (EDS), Cyclic Voltammetry (CV), and Chronoamperometry (CHA). Galvanic replacement method is utilized as a facile and spontaneous approach for growth of Pd nanostructures. The Pd-Co/G is used as an anode catalyst for ethanol oxidation in alkaline media. The Pd-Co/G not only delivered much higher current density (262.3 mAcm-2) compared to the Pd/C (32.1 mAcm-2) catalyst, but also demonstrated a negative shift of the onset oxidation potential (-0.480 vs -0.460 mV) in the forward sweep. Moreover, the novel Pd-Co/G electrocatalyst represents large electrochemically active surface area (ECSA), lower apparent activation energy (Ea), higher levels of durability and poisoning tolerance compared to the Pd/C catalyst. The paper demonstrates that the catalytic activity and stability of Pd-Co/G electrocatalyst are higher than those of the Pd/C electrocatalyst toward ethanol oxidation in alkaline media.

Keywords: thermal decomposition, nanostructures, galvanic replacement, electrocatalyst, ethanol oxidation, alkaline media

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Authors: Osamu Igawa, Hiroshi Kouchiwa, Yuji Ito

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In recent years, a reconstruction project for sewer pipelines has been progressing in Japan with the aim of renewing old sewer culverts. However, it is difficult to secure a sufficient base area for shafts in an urban area because many streets are narrow with a complex layout. As a result, construction in such urban areas is generally very demanding. In urban areas, there is a strong requirement for a safe, reliable and economical construction method that does not disturb the public’s daily life and urban activities. With this in mind, we developed a new construction method called the 'shield switching type micro-tunneling method' which integrates the micro-tunneling method and shield method. In this method, pipeline is constructed first for sections that are gently curved or straight using the economical micro-tunneling method, and then the method is switched to the shield method for sections with a sharp curve or a series of curves without establishing an intermediate shaft. This paper provides the information, features and construction examples of this newly developed method.

Keywords: micro-tunneling method, secondary lining applied RC segment, sharp curve, shield method, switching type

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Authors: S. Korkut, M. S. Kilic, E. Erhan

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In order to detect and quantify the phenolic contents of a wastewater with biosensors, two working electrodes based on modified Poly (Pyrrole) films were fabricated. Enzyme horseradish peroxidase was used as biomolecule of the prepared electrodes. Various phenolics were tested at the biosensor. Phenol detection was realized by electrochemical reduction of quinones produced by enzymatic activity. Analytical parameters were calculated and the results were compared with each other.

Keywords: carbon nanotube, phenol biosensor, polypyrrole, poly (glutaraldehyde)

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Authors: E. Popov, N. Yorino, Y. Zoka, Y. Sasaki, H. Sugihara

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This paper discusses the performance of critical trajectory method (CTrj) for power system transient stability analysis under various loading settings and heavy fault condition. The method obtains Controlling Unstable Equilibrium Point (CUEP) which is essential for estimation of power system stability margins. The CUEP is computed by applying the CTrjto the boundary controlling unstable equilibrium point (BCU) method. The Proposed method computes a trajectory on the stability boundary that starts from the exit point and reaches CUEP under certain assumptions. The robustness and effectiveness of the method are demonstrated via six power system models and five loading conditions. As benchmark is used conventional simulation method whereas the performance is compared with and BCU Shadowing method.

Keywords: power system, transient stability, critical trajectory method, energy function method

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Authors: Ksenija Milošević, Davor Lončarević, Tihana Mudrinić, Jasmina Dostanić

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Heterogeneous photocatalytic processes have gained growing interest as an efficient method to generate hydrogen by using clean energy sources and degrading various organic pollutants. The main obstacles that restrict efficient photoactivity are narrow light-response range and high rates of charge carrier recombination. The formation of heterojunction by combining a semiconductor with low VB and a semiconductor with high CB and a suitable band gap was found to be an efficient method to prepare more sensible materials with improved charge separation, appropriate oxidation and reduction ability, and enhanced visible-light harvesting. In our research, various binary heterojunction systems based on the wide-band gap (TiO₂) and narrow bandgap (g-C₃N₄, CuO, and Co₂O₃) photocatalyst were studied. The morphology, optical, and electrochemical properties of the photocatalysts were analyzed by X-ray diffraction (XRD), scanning electron microscopy (FE-SEM), N₂ physisorption, diffuse reflectance measurements (DRS), and Mott-Schottky analysis. The photocatalytic performance of the synthesized catalysts was tested in single and simultaneous systems. The synthesized photocatalysts displayed good adsorption capacity and enhanced visible-light photocatalytic performance. The mutual interactions of pollutants on their adsorption and degradation efficiency were investigated. The interfacial connection between photocatalyst constituents and the mechanism of the transport pathway of photogenerated charge species was discussed. A radical scavenger study revealed the interaction mechanisms of the photocatalyst constituents in single and multiple pollutant systems under solar and visible light irradiation, indicating the type of heterojunction system (Z scheme or type II).

Keywords: bandgap alignment, heterojunction, photocatalysis, reaction mechanism

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Authors: Serkan Sayin, Songul F. Varol

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High attention on the organic light-emitting diodes has been paid since their efficient properties in the flat panel displays, and solid-state lighting was realized. Because of their high efficient electroluminescence, brightness and providing eminent in the emission range, organic light emitting diodes have been preferred a material compared with the other materials consisting of the liquid crystal. Calixarenes obtained from the reaction of p-tert-butyl phenol and formaldehyde in a suitable base have been potentially used in various research area such as catalysis, enzyme immobilization, and applications, ion carrier, sensors, nanoscience, etc. In addition, their tremendous frameworks, as well as their easily functionalization, make them an effective candidate in the applied chemistry. Herein, a calix[4]arene derivative has been synthesized, and its structure has been fully characterized using Fourier Transform Infrared Spectrophotometer (FTIR), proton nuclear magnetic resonance (¹H-NMR), carbon-13 nuclear magnetic resonance (¹³C-NMR), liquid chromatography-mass spectrometry (LC-MS), and elemental analysis techniques. The calixarene derivative has been employed as an emitting layer in the fabrication of the organic light-emitting diodes. The optical and electrochemical features of calixarane-contained organic light-emitting diodes (Clx-OLED) have been also performed. The results showed that Clx-OLED exhibited blue emission and high external quantum efficacy. As a conclusion obtained results attributed that the synthesized calixarane derivative is a promising chromophore with efficient fluorescent quantum yield that provides it an attractive candidate for fabricating effective materials for fluorescent probes and labeling studies. This study was financially supported by the Scientific and Technological Research Council of Turkey (TUBITAK Grant no. 117Z402).

Keywords: calixarene, OLED, supramolecular chemistry, synthesis

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Authors: Nouf M. Al-Ourfi, A. S. Bashammakh, M. S. El-Shahawi

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The redox behavior of dianabol steroid (DS) on Nafion Multiwalled Carbon nano -tubes (MWCNT) composite film modified glassy carbon electrode (GCE) in various buffer solutions was studied using cyclic voltammetry (CV) and differential pulse- adsorptive cathodic stripping voltammetry (DP-CSV) and successfully compared with the results at non modified bare GCE. The Nafion-MWCNT composite film modified GCE exhibited the best electrochemical response among the two electrodes for the electro reduction of DS that was inferred from the EIS, CV and DP-CSV. The modified sensor showed a sensitive, stable and linear response in the concentration range of 5 – 100 nM with a detection limit of 0.08 nM. The selectivity of the proposed sensor was assessed in the presence of high concentration of major interfering species. The analytical application of the sensor for the quantification of DS in pharmaceutical formulations and biological fluids (urine) was determined and the results demonstrated acceptable recovery and RSD of 5%. Statistical treatment of the results of the proposed method revealed no significant differences in the accuracy and precision. The relative standard deviations for five measurements of 50 and 300 ng mL−1 of DS were 3.9 % and 1.0 %, respectively.

Keywords: dianabol steroid, determination, modified GCE, urine

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Authors: Bing–Jing Zhao, Chang-Kui Liu, Hong Wang, Min Hu

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Electron beam rapid manufacturing (EBRM) or Selective laser melting is an additive manufacturing process that uses 3D CAD data as a digital information source and energy in the form of a high-power laser beam or electron beam to create three-dimensional metal parts by fusing fine metallic powders together.Object:The present study was conducted to evaluate the mechanical properties ,the phase transformation,the corrosivity and the biocompatibility of Ti-6Al-4V by EBRM,SLM and forging technique.Method: Ti-6Al-4V alloy standard test pieces were manufactured by EBRM, SLM and forging technique according to AMS4999,GB/T228 and ISO 10993.The mechanical properties were analyzed by universal test machine. The phase transformation was analyzed by X-ray diffraction and scanning electron microscopy. The corrosivity was analyzed by electrochemical method. The biocompatibility was analyzed by co-culturing with mesenchymal stem cell and analyzed by scanning electron microscopy (SEM) and alkaline phosphatase assay (ALP) to evaluate cell adhesion and differentiation, respectively. Results: The mechanical properties, the phase transformation, the corrosivity and the biocompatibility of Ti-6Al-4V by EBRM、SLM were similar to forging and meet the mechanical property requirements of AMS4999 standard. a­phase microstructure for the EBM production contrast to the a’­phase microstructure of the SLM product. Mesenchymal stem cell adhesion and differentiation were well. Conclusion: The property of the Ti-6Al-4V alloy manufactured by EBRM and SLM technique can meet the medical standard from this study. But some further study should be proceeded in order to applying well in clinical practice.

Keywords: 3D printing, Electron Beam Rapid Manufacturing (EBRM), Selective Laser Melting (SLM), Computer Aided Design (CAD)

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