Search results for: electrochemical separation

Authors: Nice Vasconcelos Coimbra, Fábio dos Santos Gonçalves, Marisa Nascimento, Ellen Cristine Giese

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The development of chemical routes for the recovery and separation of rare earth elements (REE) is seen as a priority and strategic action by several countries demanding these elements. Among the possibilities of alternative routes, the biosorption process has been evaluated in our laboratory. In this theme, the present work attempts to assess and fit the solution equilibrium data in Langmuir, Freundlich and DKR isothermal models, based on the biosorption results of the lanthanum and samarium elements by Bacillus subtilis immobilized on calcium alginate gel. It was observed that the preference of adsorption of REE by the immobilized biomass followed the order Sm (III)> La (III). It can be concluded that among the studied isotherms models, the Langmuir model presented better mathematical results than the Freundlich and DKR models.

Keywords: rare earth elements, biosorption, Bacillus subtilis, adsorption isotherm models

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Authors: T. Abohalkuma, J. Telegdi

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Preparation, characterization, and application of self-assembled monolayers (SAM) formed by fluorophosphonic and undecenyl phosphonic acids on carbon steel surfaces as anticorrosive nanocoatings were demonstrated. The anticorrosive efficacy of these SAM layers was followed by atomic force microscopy, as the change in the surface morphology caused by layer deposition and corrosion processes was monitored. The corrosion process was determined by electrochemical potentiodynamic polarization, whereas the surface wettability of the carbon steel samples was tested with the use of static and dynamic contact angle measurements. Results showed that both chemicals produced good protection against corrosion as they performed as anodic inhibitors, especially with increasing the time of layer formation, which results in a more compact molecular film. According to the atomic force microscope (AFM) images, the fluoro-phosphonic acid self-assembled molecular layer can control the general as well as the pitting corrosion, but the SAM layers of the undecenyl-phosphonic acid cannot inhibit the pitting corrosion. The AFM and the contact angle measurements confirmed the results achieved by electrochemical measurements.

Keywords: nanolayers, corrosion, phosphonic acids, coatings

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Authors: Rinlee Butch M. Cervera, Princess Stephanie P. Llanos

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Lithium iron phosphate (LiFePO₄) is a potential cathode material for lithium-ion batteries due to its promising characteristics. In this study, pure LiFePO₄ (LFP) and carbon-coated nanograined LiFePO₄ (LFP-C) is synthesized and characterized for its microstructural properties. X-ray diffraction patterns of the synthesized samples can be indexed to an orthorhombic LFP structure with about 63 nm crystallite size as calculated by using Scherrer’s equation. Agglomerated particles that range from 200 nm to 300 nm are observed from scanning electron microscopy images. Transmission electron microscopy images confirm the crystalline structure of LFP and coating of amorphous carbon layer. Elemental mapping using energy dispersive spectroscopy analysis revealed the homogeneous dispersion of the compositional elements. In addition, galvanostatic charge and discharge measurements were investigated for the cathode performance of the synthesized LFP and LFP-C samples. The results showed that the carbon-coated sample demonstrated the highest capacity of about 140 mAhg^-1 as compared to non-coated and micrograined sized commercial LFP.

Keywords: ceramics, energy storage, electrochemical measurements, transmission electron microscope

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Authors: Francis Mark A. Fernandez, Chelca Ubay, Armithan Suguitan

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Regions or provinces in a definite state certainly contribute to the economy of their mainland. These regions or provinces are the ones supplying the mainland with different resources and assets. Thus, with a certain region separating from the mainland would indeed impinge the heart of an entire state to develop and expand. With these, the researchers decided to study on the effects of the separation of one’s region to its mainland and the consequences that will take place if the mainland would rule out the region to separate from them. The researchers wrote this paper to present the causes of the separation of Catalonia from Spain and the prediction regarding the pursuance of this region to revolt from its mainland, Spain. In conducting this research, the researchers utilized two analyses, namely: qualitative and quantitative. In qualitative, numerous of information regarding the existing experiences of the citizens of Catalonia were gathered by the authors to give certainty to the prediction of the researchers. Besides this undertaking, the researchers will also gather needed information and figures through books, journals and the published news and reports. In addition, to further support this prediction under qualitative analysis, the researchers intended to operate the Phenomenological research in which the examiners will exemplify the lived experiences of each citizen in Catalonia. Moreover, the researchers will utilize one of the types of Phenomenological research which is hermeneutical phenomenology by Van Manen. In quantitative analysis, the researchers utilized the regression analysis in which it will ascertain the causality in an underlying theory in understanding the relationship of the variables. The researchers assigned and identified different variables, wherein the dependent variable or the y which represents the prediction of the researchers, the independent variable however or the x represents the arising problems that grounds the partition of the region, the summation of the independent variable or the ∑x represents the sum of the problem and finally the summation of the dependent variable or the ∑y is the result of the prediction. With these variables, using the regression analysis, the researchers will be able to show the connections and how a single variable could affect the other variables. From these approaches, the prediction of the researchers will be specified. This research could help different states dealing with this kind of problem. It will further help certain states undergoing this problem by analyzing the causes of these insurgencies and the effects on it if it will obstruct its region to consign their full-pledge autonomy.

Keywords: autonomy, liberty, prediction, separation

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Authors: Ratna Dewi Kusumaningtyas, Riris Pristiyani, Heny Dewajani

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Biodiesel is commonly produced via the two main routes, i.e. the transesterification of triglycerides and the esterification of free fatty acid (FFA) using short-chain alcohols. Both the two routes have drawback in term of the side product yielded during the reaction. Transesterification reaction of triglyceride results in glycerol as side product. On the other hand, FFA esterification brings in water as side product. Both glycerol and water in the biodiesel production are managed as waste. Hence, a separation process is necessary to obtain a high purity biodiesel. Meanwhile, separation processes is generally the most capital and energy intensive part in industrial process. Therefore, to reduce the separation process, it is essential to produce biodiesel via an alternative route eliminating glycerol or water side-products. In this work, biodiesel synthesis was performed using a glycerol-free process through chemical interesterification of jatropha oil with ethyl acetate in the presence on sodium acetate catalyst. By using this method, triacetine, which is known as fuel bio-additive, is yielded instead of glycerol. This research studied the effects of catalyst concentration on the jatropha oil interesterification process in the range of 0.5 – 1.25% w/w oil. The reaction temperature and molar ratio of oil to ethyl acetate were varied at 50, 60, and 70°C, and 1:6, 1:9, 1:15, 1:30, and 1:60, respectively. The reaction time was evaluated from 0 to 8 hours. It was revealed that the best yield was obtained with the catalyst concentration of 0.5%, reaction temperature of 70 °C, molar ratio of oil to ethyl acetate at 1:60, at 6 hours reaction time.

Keywords: biodiesel, interesterification, glycerol-free, triacetine, jatropha oil

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Authors: Gopal Ji, Priyanka Dwivedi, Shanthi Sundaram, Rajiv Prakash

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Inhibition effect of aqueous Argemone Mexicana root extract (AMRE) on mild steel corrosion in 1 M HCl has been studied by weight loss, Tafel polarization curves, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. Results indicate that inhibition ability of AMRE increases with the increasing amount of the extract. A maximum corrosion inhibition of 94% is acknowledged at the extract concentration of 400 mg L-1. Polarization curves and impedance spectra reveal that both cathodic and anodic reactions are suppressed due to passive layer formation at metal-acid interface. It is also confirmed by SEM micro graphs and FTIR studies. Furthermore, the effects of acid concentration (1-5 M), immersion time (120 hours) and temperature (30-60˚C) on inhibition potential of AMRE have been investigated by weight loss method and electrochemical techniques. Adsorption mechanism is also proposed on the basis of weight loss results, which shows good agreement with Langmuir isotherm.

Keywords: mild steel, polarization, SEM, acid corrosion, EIS, green inhibition

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Authors: Srinivasa Reddy Mallampati, Min Hee Park, Soo Mim Cho, Sung Hyeon Yoon

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One of the issues of End of Life Vehicles (ELVs) recycling promotion is technology for the appropriate treatment of automotive shredder residue (ASR). Owing to its high heterogeneity and variable composition (plastic (23–41%), rubber/elastomers (9–21%), metals (6–13%), glass (10–20%) and dust (soil/sand) etc.), ASR can be classified as ‘hazardous waste’, on the basis of the presence of heavy metals (HMs), PCBs, BFRs, mineral oils, etc. Considering their relevant concentrations, these metals and plastics should be properly recovered for recycling purposes before ASR residues are disposed of. Brominated flame retardant additives in ABS/HIPS and PVC may generate dioxins and furans at elevated temperatures. Moreover, these BFRs additives present in plastic materials may leach into the environment during landfilling operations. ASR thermal process removes some of the organic material but concentrates, the heavy metals and POPs present in the ASR residues. In the present study, Fe/Ca/CaO nanoparticle assisted ozone treatment has been found to selectively hydrophilize the surface of ABS/HIPS and PVC plastics, enhancing its wettability and thereby promoting its separation from ASR plastics by means of froth flotation. The water contact angles, of ABS/HIPS and PVC decreased, about 18.7°, 18.3°, and 17.9° in ASR respectively. Under froth flotation conditions at 50 rpm, about 99.5% and 99.5% of HIPS in ASR samples sank, resulting in a purity of 98% and 99%. Furthermore, at 150 rpm a 100% PVC separation in the settled fraction, with 98% of purity in ASR, respectively. Total recovery of non-ABS/HIPS and PVC plastics reached nearly 100% in the floating fraction. This process improved the quality of recycled ASR plastics by removing surface contaminants or impurities. Further, a hybrid ball-milling and with Fe/Ca/CaO nanoparticle froth flotation process was established for the recovery of HMs from ASR. After ball-milling with Fe/Ca/CaO nanoparticle additives, the flotation efficiency increased to about 55 wt% and the HMs recovery were also increased about 90% for the 0.25 mm size fractions of ASR. Coating with Fe/Ca/CaO nanoparticles associated with subsequent microbubble froth flotation allowed the air bubbles to attach firmly on the HMs. SEM–EDS maps showed that the amounts of HMs were significant on the surface of the floating ASR fraction. This result, along with the low HM concentration in the settled fraction, was confirmed by elemental spectra and semi-quantitative SEM–EDS analysis. Developed hybrid preferential hazardous plastics and metals separation process from ASR is a simple, highly efficient, and sustainable procedure.

Keywords: end of life vehicles shredder residue, hazardous plastics, nanoparticle froth flotation, separation process

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Authors: Hassiba Benguergoura, Kamal Chanane, Sâad Moulay

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Pervaporation (PV), a membrane-based separation technology, has gained much attention because of its energy saving capability and low-cost, especially for separation of azeotropic or close-boiling liquid mixtures. There are two crucial issues for industrial application of pervaporation process. The first is developing membrane material and tailoring membrane structure to obtain high pervaporation performances. The second is modeling pervaporation transport to better understand of the above-mentioned structure–pervaporation relationship. Many models were proposed to predict the mass transfer process, among them, solution-diffusion model is most widely used in describing pervaporation transport including preferential sorption, diffusion and evaporation steps. For modeling pervaporation transport, the permeation flux, which depends on the solubility and diffusivity of components in the membrane, should be obtained first. Traditionally, the solubility was calculated according to the Flory–Huggins theory. Separation of the benzene (Bz)/cyclohexane (Cx) mixture is industrially significant. Numerous papers have been focused on the Bz/Cx system to assess the PV properties of membrane materials. Membranes with both high permeability and selectivity are desirable for practical application. Several new polymers have been prepared to get both high permeability and selectivity. Styrene-butadiene rubbers (SBR), dense membranes cross-linked by chloromethylation were used in the separation of benzene/cyclohexane mixtures. The impact of chloromethylation reaction as a new method of cross-linking SBR on the pervaporation performance have been reported. In contrast to the vulcanization with sulfur, the cross-linking takes places on styrene units of polymeric chains via a methylene bridge. The partial pervaporative (PV) fluxes of benzene/cyclohexane mixtures in styrene-butadiene rubber (SBR) were predicted using Fick's first law. The predicted partial fluxes and the PV separation factor agreed well with the experimental data by integrating Fick's law over the benzene concentration. The effects of feed concentration and operating temperature on the predicted permeation flux by this proposed model are investigated. The predicted permeation fluxes are in good agreement with experimental data at lower benzene concentration in feed, but at higher benzene concentration, the model overestimated permeation flux. The predicted and experimental permeation fluxes all increase with operating temperature increasing. Solvent sorption levels for benzene/ cyclohexane mixtures in a SBR membrane were determined experimentally. The results showed that the solvent sorption levels were strongly affected by the feed composition. The Flory- Huggins equation generates higher R-square coefficient for the sorption selectivity.

Keywords: benzene, cyclohexane, pervaporation, permeation, sorption modeling, SBR

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Authors: Imtiaz Ahmed Khan, Sabu John, Sania Waqar, Lijing Wang, Mac Fergusson, Ilija Najdovski

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Evolution of textiles, from its orthodox to more interactive role has stirred the researchers to uncover its application in numerous arenas. The idea of using textile based materials for wearable energy harvesting and storage devices have gained immense popularity. This is mainly due to textile comfort and flexibility features. In this work, nano-carbonous materials were infused on cellulosic fibers using caustic soda treatment. This paper presents the complete procedure of yarn supercapacitors fabrication process through dip coating technique and its characterization method. The main objective is to study, the effect of varying caustic soda concentration on mass loading of activated carbon on yarns and the related capacitance output of the designed yarn supercapacitor. Polyvinyl alcohol and Phosphoric acid were used as electrolyte in a two-electrode cell assembly to measure device electrochemical performance. The results show a promising increase in capacitance value using this technique.

Keywords: yarn supercapacitors, activated carbon, dip coating, caustic soda, electrolyte, electrochemical characterization

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Authors: A. Asselah, A. Khalfi, M. A.Toumi, A.Tazerouti

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The study of the corrosion inhibition of a standard carbon steel "API 5L grade X70" by two biodegradable anionic surfactants derived from fatty acids by photo sulfochlorination, called sodium lauryl methyl ester sulfonates and sodium palmityl methyl ester sulfonates was carried. A solution at 2.5 g/l NaCl saturated with carbon dioxide is used as a corrosive medium. The gravimetric and electrochemical technics (stationary and transient) were used in order to quantify the rate of corrosion and to evaluate the electrochemical inhibition efficiency, thus the nature of the mode of action of the inhibitor, in addition to a surface characterization by scanning electron microscopy (MEB) coupled to energy dispersive X-ray spectroscopy (EDX). The variation of the concentration and the temperature were examined, and the mode of adsorption of these inhibitors on the surface of the metal was established by assigning it the appropriate isotherm and determining the corresponding thermodynamic parameters. The MEB-EDX allowed the visualization of good adhesion of the protective film formed by the surfactants to the surface of the steel. The corrosion inhibition was evaluated at around 93% for sodium lauryl methyl ester sulfonate surfactant at 20 ppm and 87.2% at 50 ppm for sodium palmityl methyl ester sulfonate surfactant.

Keywords: carbon steel, oilfield, corrosion, anionic surfactants

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Authors: S. Pradhan, V. Kumaran

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Centrifugal gas separation processes effect separation by utilizing the difference in the mole fraction in a high speed rotating cylinder caused by the difference in molecular mass, and consequently the centrifugal force density. These have been widely used in isotope separation because chemical separation methods cannot be used to separate isotopes of the same chemical species. More recently, centrifugal separation has also been explored for the separation of gases such as carbon dioxide and methane. The efficiency of separation is critically dependent on the secondary flow generated due to temperature gradients at the cylinder wall or due to inserts, and it is important to formulate accurate models for this secondary flow. The widely used Onsager model for secondary flow is restricted to very long cylinders where the length is large compared to the diameter, the limit of high stratification parameter, where the gas is restricted to a thin layer near the wall of the cylinder, and it assumes that there is no mass difference in the two species while calculating the secondary flow. There are two objectives of the present analysis of the rarefied gas flow in a rotating cylinder. The first is to remove the restriction of high stratification parameter, and to generalize the solutions to low rotation speeds where the stratification parameter may be O (1), and to apply for dissimilar gases considering the difference in molecular mass of the two species. Secondly, we would like to compare the predictions with molecular simulations based on the direct simulation Monte Carlo (DSMC) method for rarefied gas flows, in order to quantify the errors resulting from the approximations at different aspect ratios, Reynolds number and stratification parameter. In this study, we have obtained analytical and numerical solutions for the secondary flows generated at the cylinder curved surface and at the end-caps due to linear wall temperature gradient and external gas inflow/outflow at the axis of the cylinder. The effect of sources of mass, momentum and energy within the flow domain are also analyzed. The results of the analytical solutions are compared with the results of DSMC simulations for three types of forcing, a wall temperature gradient, inflow/outflow of gas along the axis, and mass/momentum input due to inserts within the flow. The comparison reveals that the boundary conditions in the simulations and analysis have to be matched with care. The commonly used diffuse reflection boundary conditions at solid walls in DSMC simulations result in a non-zero slip velocity as well as a temperature slip (gas temperature at the wall is different from wall temperature). These have to be incorporated in the analysis in order to make quantitative predictions. In the case of mass/momentum/energy sources within the flow, it is necessary to ensure that the homogeneous boundary conditions are accurately satisfied in the simulations. When these precautions are taken, there is excellent agreement between analysis and simulations, to within 10 %, even when the stratification parameter is as low as 0.707, the Reynolds number is as low as 100 and the aspect ratio (length/diameter) of the cylinder is as low as 2, and the secondary flow velocity is as high as 0.2 times the maximum base flow velocity.

Keywords: rotating flows, generalized onsager and carrier-Maslen model, DSMC simulations, rarefied gas flow

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Authors: Abdi Djamila, Haffar Hichem

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The poly methylene bleu (PMB) has been successfully electro deposited on fluorine doped tin oxide (FTO) conducting glass as substrate. Its optical, electrical and photoelectrochemical characterizations have been carried out in order to show the performances of such polymer. The deposited film shows a good electric conductivity which is well confirmed by the low gap value determinated optically by UV–vis spectroscopy. Like all polymers the PMB presents an absorption difference in the visible range function of the polarization potential, it is expressed by the strong conjugation at oxidized state but is weakened with leucoform formation at reduced state. The electrochemical analysis of the films permit to show the cyclic voltamperogram with the anodic oxidation and cathodic reduction states of the polymer and to locate the corresponding energy levels HOMO and LUMO of this later. The electrochemical impedance spectroscopy permit to see the conductive character of such film and to calculate important parameters as Rtc and CPE. The study of the photoelectro activity of our polymer shows that under exposure to intermittent light source this later exhibit important photocurrents which enables it to be used in photo organic ells.

Keywords: polymethylene blue, electropolymerization, homo-lumo, photocurrents

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Authors: M. Deyab, A. Al-Sabagh, S. Keera

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The effects of flow velocity, sand concentration, sand size and temperature on erosion-corrosion of carbon steel in oil sands slurry were studied by electrochemical polarization measurements. It was found that the anodic excursion spans of carbon steel in oil sands slurry are characterized by the occurrence of a well-defined anodic peak, followed by a passive region. The data reveal that increasing flow velocity, sand concentration and temperature enhances the anodic peak current density (jAP) and shifts pitting potential (Epit) towards more negative values. The variation of sand particle size does not have apparent effect on polarization behavior of carbon steel. The ratios of the erosion rate to corrosion rate (E/C) were calculated and discussed. The ratio of erosion to corrosion rates E/C increased with increasing the flow velocity, sand concentration, sand size and temperature indicating that an increasing slurry flow velocity, sand concentration, sand size and temperature resulted in an enhancement of the erosion effect.

Keywords: erosion-corrosion, steel, oil sands slurry, polarization

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Authors: Mohsen Adabi, Mahdi Adabi, Reza Saber

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The recent advancements in nanomaterials have provided a platform to develop efficient transduction matrices for sensors. Modified electrodes allow to electrochemists to enhance the property of electrode surface and provide desired properties such as improved sensing capabilities, higher electron transfer rate and prevention of undesirable reactions competing kinetically with desired electrode process. Nanostructured electrodes including arrays of carbon nanotubes have demonstrated great potential for the development of electrochemical sensors and biosensors. The aim of this work is to evaluate the concentration of multi-walled carbon nanotubes (MWCNTs) on the conductivity of gold electrode. For this work, raw MWCNTs was functionalized and shortened. Raw and shorten MWCNTs were characterized using transfer electron microscopy (TEM). Next, 0.5, 2 and 3.5 mg of Shortened and functionalized MWCNTs were dispersed in 2 mL Dimethyl formamide (DMF) and cysteamine modified gold electrodes were incubated in the different concentrations of MWCNTs for 8 hours. Then, the immobilization of MWCNTs on cysteamine modified gold electrode was characterized by scanning electron microscopy (SEM) and the effect of MWCNT concentrations on electron transfer of modified electrodes was investigated by cyclic voltammetry (CV). The results demonstrated that CV response of ferricyanide redox at modified gold electrodes increased as concentration of MWCNTs enhanced from 0.5 to 2 mg in 2 mL DMF. This increase can be attributed to the number of MWCNTs which enhance on the surface of cysteamine modified gold electrode as the MWCNTs concentration increased whereas CV response of ferricyanide redox at modified gold electrodes did not changed significantly as the MWCNTs concentration increased from 2 to 3.5 mg in 2 mL DMF. The reason may be that amine groups of cysteamine modified gold electrodes are limited to a given number which can interact with the given number of carboxylic groups of MWCNTs and CV response of ferricyanide redox at modified gold do not enhance after amine groups of cysteamine are saturated with carboxylic groups of MWCNTs.

Keywords: carbon nanotube, cysteamine, electrochemical sensor, gold electrode

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Authors: Gregory Schmidt

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Solid-state lithium batteries are broadly accepted as promising candidates for application in the next generation of EVs as they should offer safer and higher-energy-density batteries. Nonetheless, their development is impeded by many challenges, including the resistive electrode–electrolyte interface originating from the removal of the liquid electrolyte that normally permeates through the porous cathode and ensures efficient ionic conductivity through the cell. One way to tackle this challenge is by formulating composite cathodes containing solid ionic conductors in their structure, but this approach will require the conductors to exhibit chemical stability, electrochemical stability, flexibility, and adhesion and is, therefore, limited to some materials. Recently, Arkema developed a technology called buffering layer which allows the transformation of any conventional porous electrode into a catholyte. This organic layer has a very high ionic conductivity at room temperature, is compatible with all active materials, and can be processed with conventional Gigafactory equipment. Moreover, this layer helps protect the solid ionic conductor from the cathode and anode materials. During this presentation, the manufacture and the electrochemical performance of this layer for different systems of cathode and anode will be discussed.

Keywords: electrochemistry, all solid state battery, materials, interface

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Authors: Princess Stephanie P. Llanos, Rinlee Butch M. Cervera

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Lithium iron phosphate (LiFePO4) is a potential cathode material for lithium-ion batteries due to its promising characteristics. In this study, carbon-coated nanograined LiFePO4 is synthesized via wet chemistry method at a low temperature of 400 °C and investigated its performance as a cathode in Lithium battery. The X-ray diffraction pattern of the synthesized samples can be indexed to an orthorhombic LiFePO4 structure. Agglomerated particles that range from 200 nm to 300 nm are observed from scanning electron microscopy images. Transmission electron microscopy images confirm the crystalline structure of LiFePO4 and coating of amorphous carbon layer. Elemental mapping using Energy dispersive spectroscopy analysis revealed the homogeneous dispersion of Fe, P, O, and C elements. On the other hand, the electrochemical performances of the synthesized cathodes were investigated using cyclic voltammetry, galvanostatic charge/discharge tests with different C-rates, and cycling performances. Galvanostatic charge and discharge measurements revealed that the sample sintered at 400 °C for 3 hours with carbon coating demonstrated the highest capacity among the samples which reaches up to 160 mAhg⁻¹ at 0.1C rate.

Keywords: cathode, charge-discharge, electrochemical, lithium batteries

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Authors: Sajjad Esmaeili, Robert Krause, Lukas Gerlich, Alireza Mohammadian Kia, Benjamin Uhlig

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This investigation aims to develop the feasible and qualitative process parameters for the thin films fabrication into ultra-large through-silicon-vias (TSVs) as vertical interconnections. The focus of the study is on TSV metallization and its challenges employing new materials for the purpose of rapid signal propagation in the microsystems technology. Cobalt metal-organic chemical vapor deposition (Co-MOCVD) process enables manufacturing an adhesive and excellent conformal ultra-thin film all the way through TSVs in comparison with the conventional non-conformal physical vapor deposition (PVD) process of copper (Cu) seed layer. Therefore, this process provides a Cu seed-free layer which is capable of direct Cu electrochemical deposition (Cu-ECD) on top of it. The main challenge of this metallization module is to achieve the proper alternative seed layer with less roughness, sheet resistance and granular organic contamination (e.g. carbon) which intensify the Co corrosion under the influence of Cu electrolyte.

Keywords: Cobalt MOCVD, direct Cu electrochemical deposition (ECD), metallization technology, through-silicon-via (TSV)

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Authors: Hanene Akrout, Ines Elaissaoui, Sabrina Grassini, Daniele Fulginiti, Latifa Bousselmi

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The main objective of this work is to investigate the efficiency of depollution power related to PbO₂ layer deposited onto a stainless steel (SS) substrate with SiOx as interlayer. The elaborated electrode was used as anode for anodic oxidation of wastewater containing Amaranth dye, as recalcitrant organic pollutant model. SiOx interlayer was performed using Plasma Enhanced Chemical Vapor Deposition ‘PECVD’ in plasma fed with argon, oxygen, and tetraethoxysilane (TEOS, Si precursor) in different ratios, onto the SS substrate. PbO₂ layer was produced by pulsed electrodeposition on SS/SiOx. The morphological of different surfaces are depicted with Field Emission Scanning Electron Microscope (FESEM) and the composition of the lead oxide layer was investigated by X-Ray Diffractometry (XRD). The results showed that the SiOx interlayer with more rich oxygen content improved better the nucleation of β-PbO₂ form. Electrochemical Impedance Spectroscopy (EIS) measurements undertaken on different interfaces (at optimized conditions) revealed a decrease of Rfilm while CPE film increases for SiOx interlayer, characterized by a more inorganic nature and deposited in a plasma fed by higher O2-to-TEOS ratios. Quantitative determinations of the Amaranth dye degradation rate were performed in terms of colour and COD removals, reaching a 95% and an 80% respectively removal at pH = 2 in 300 min. Results proved the improvement of the degradation wastewater containing the amaranth dye. During the electrolysis, the Amaranth dye solution was sampled at 30 min intervals and analyzed by ‘High-performance Liquid Chromatography’ HPLC. The gradual degradation of the Amaranth dye confirmed by the decrease in UV absorption using the SS/SiOx(20:20:1)/PbO₂ anode, the reaction exhibited an apparent first-order kinetic for electrolysis time of 5 hours, with an initial rate constant of about 0.02 min⁻¹.

Keywords: electrochemical treatment, PbO₂ anodes, COD removal, plasma

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Authors: Cassandra Seery

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During the twentieth century, the notion of child rights at the international level began with the League of Nations’ Geneva Declaration of the Rights of the Child 1924, culminating in the development and adoption of the UN Convention on the Rights of the Child (‘the Convention’) in 1989. A key foundation of child rights lies in the development of the ‘best interests of the child’ principle and its subsequent incorporation into domestic legislation across the globe. This principle has become a key concept in child rights protection and has become a widely recognized principle in the protection of child rights. However, despite its status as the primary operating standard in child and family law and its ‘deepening hold in domestic and international instruments’, the meaning of the ‘best interests of the child’ principle has been criticised as open-ended and vague. This paper explores the evolution and development of the principle in the context of parental separation at international law throughout the 21st century and identifies opportunities for the Nation States to further improve legislative responses in associated child protection cases. An extensive review of relevant United Nations documentation (including instruments, resolutions and comments, jurisprudence, reports, guidelines and policies, training materials and so forth) explores: (i) what progress has been made to further develop the principle at the international level with regard to parental separation; and (ii) what developments participating the Nation States should consider as part of future legal and social policy reforms in this space. It will highlight opportunities for improvement and explore the benefit and relevance of international approaches for the Nation States moving forward.

Keywords: international human rights, best interests of the child, legal and social policy, child rights

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Authors: Kul Pun, F. A. Hamad, T. Ahmed, J. O. Ugwu, J. Eyers, G. Lawson, P. A. Russell

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Determining droplet size and distribution is essential when determining the separation efficiency of a two/three-phase separator. This paper investigates the effect of liquid flow and oil pad thickness on the droplet size at the lab scale. The findings show that increasing the inlet flow rates of the oil and water results in size reduction of the droplets and increasing the thickness of the oil pad increases the size of the droplets. The data were fitted with a simple Gaussian model, and the parameters of mean, standard deviation, and amplitude were determined. Trends have been obtained for the fitted parameters as a function of the Reynolds number, which suggest a way forward to better predict the starting parameters for population models when simulating separation using CFD packages. The key parameter to predict to fix the position of the Gaussian distribution was found to be the mean droplet size.

Keywords: two-phase separator, average bubble droplet, bubble size distribution, liquid-liquid phase

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Authors: Jorge Santos, Ana V. Girão, F. J. Oliveira, Alexandre C. Bastos

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Protective or decorative coatings containing hexavalent chromium compounds are still used on metal and plastic parts. These hexavalent chromium compounds represent a risk to living beings and the environment, and, for this reason, there is a great need to investigate alternatives. Physical Vapor Deposition (PVD) is an environmentally friendly process that allows the deposition of wear and corrosion resistant thin films with excellent optical properties. However, PVD thin films are porous and if deposited onto low corrosion resistant substrates, lead to a degradation risk. The corrosion behavior of chromium-free electroplated coating systems finished with magnetron sputtered PVD thin films was investigated in this work. The electroplated systems consisted of distinct nickel layers deposited on top of a copper interlayer on acrylonitrile butadiene styrene (ABS) plates. Electrochemical and corrosion evaluation was conducted by electrochemical impedance spectroscopy and polarization curves on the different electroplated coating systems, with and without PVD thin film on top. The results show that the corrosion resistance is lower for the electroplated coating systems finished with PVD thin film for extended exposure periods when compared to those without the PVD overlay.

Keywords: PVD, electroplating, corrosion, thin film

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Authors: Rupan Das Chakraborty, Surendra K. Martha

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Hard carbons (HCs) are extensively used as anode materials for sodium-ion batteries due to their availability, low cost, and ease of synthesis. It possesses the ability to store Na ion between stacked sp2 carbon layers and micropores. In this work, hard carbons are synthesized from different concentrations (0.5M to 5M) of dextrose solutions by hydrothermal synthesis followed by high-temperature calcination at 1100 ⁰C in an inert atmosphere. Dextrose has been chosen as a precursor material as it is a eco-friendly and renewable source. Among all hard carbon derived from different concentrations of dextrose solutions, hard carbon derived from 3M dextrose solution delivers superior electrochemical performance compared to other hard carbons. Hard carbon derived from 3M dextrose solution (Dextrose derived Hard Carbon-3M) provides an initial reversible capacity of 257 mAh g-1 with a capacity retention of 83 % at the end of 100 cycles at 30 mA g-1). The carbons obtained from different dextrose concentration show very similar Cyclic Voltammetry and chargedischarging behavior at a scan rate of 0.05 mV s-1 the Cyclic Voltammetry curve indicate that solvent reduction and the solid electrolyte interface (SEI) formation start at E < 1.2 V (vs Na/Na+). Among all 3M dextrose derived electrode indicate as a promising anode material for Sodium-ion batteries (SIBs).

Keywords: dextrose derived hard carbon, anode, sodium-ion battery, electrochemical performance

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Authors: Seung Moon Woo, Youn Suk Chung, Sang Yong Nam

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In the present time, we need advanced water treatment technology for separation of virus and bacteria in effluent which occur epidemic and waterborne diseases. Water purification system is mainly divided into two categorizations like reverse osmosis (RO) and ultrafiltration (UF). Membrane used in these systems requires higher durability because of operating in harsh condition. Of these, the membrane using in UF system has many advantages like higher efficiency and lower energy consume for water treatment compared with RO system. In many kinds of membrane, hollow fiber type membrane is possible to make easily and to get optimized property by control of various spinning conditions such as temperature of coagulation bath, concentration of polymer, addition of additive, air gap and internal coagulation. In this study, polysulfone hollow fiber membrane was successfully prepared by phase inversion method for separation of virus and bacteria. When we prepare the hollow fiber membrane, we controlled various factors such as the polymer concentration, air gap and internal coagulation to investigate effect to membrane property. Morphology of surface and cross section of membrane were measured by field emission scanning electron microscope (FE-SEM). Water flux of membrane was measured using test modules. Mean pore diameter of membrane was calculated using rejection of polystyrene (PS) latex beads for separation of virus and bacteria. Flux and mean flow pore diameter of prepared membrane show 1.5 LPM, 0.03 μm at 1.0 kgf/cm2. The bacteria and virus removal performance of prepared UF membranes were over 6 logs.

Keywords: hollow fiber membrane, drinking water, ultrafiltration, bacteria

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Authors: Rosmini Yanti, Safira Aviolita, Marsetio

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Indonesia has several straits that are very important as a shipping lane, including the Sunda Strait and the Lombok Strait, which are the part of the Indonesian Archipelagic Sea Lane (IASL). An increase in traffic on the Marine Archipelago makes the task of monitoring sea routes increasingly difficult. Indonesia has proposed the establishment of a Traffic Separation Scheme (TSS) in the Sunda Strait and the Lombok Strait and the country now has the right to be able to conceptualize the TSS as well as the obligation to regulate it. Indonesia has the right to maintain national safety and sovereignty. In setting the TSS, Indonesia needs to issue national regulations that are in accordance with international law and the general provisions of the IMO (International Maritime Organization) can then be used as guidelines for maritime safety and security in the Sunda Strait and the Lombok Strait. The research method used is a qualitative method with the concept of linguistic and visual data collection. The source of the data is the analysis of documents and regulations. The results show that the determination of TSS was justified by International Law, in accordance with article 22, article 41, and article 53 of the United Nations Convention on the Law of the Sea (UNCLOS) 1982. The determination of TSS by the Indonesian government would be in accordance with COLREG (International Convention on Preventing Collisions at Sea) 10, which has been designed to follow IASL. Thus, TSS can provide a function as a safety and monitoring medium to minimize ship accidents or collisions, including the warship and aircraft of other countries that cross the IASL.

Keywords: archipelago state, maritime law, maritime security, traffic separation scheme

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Authors: Onyinyechi Lilian Uche

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Limiting arbitrariness and political power in governance is expressed in the concept of constitutionalism. Constitutionalism acknowledges the necessity for government but insists upon a limitation being placed upon its powers. It is therefore clear that the essence of constitutionalism is obviation of arbitrariness in governance and maximisation of liberty with adequate and expedient restraint on government. The doctrine of separation of powers accompanied by a system of checks and balances in Nigeria like many other African countries is marked by elements of ‘personal government’ and this has raised questions about whether the apparent separation of powers provided for in the Nigerian Constitution is not just a euphemism for the hegemony of the executive over the other two arms of government; the legislature and the judiciary. Another question raised in the article is whether the doctrine is merely an abstract philosophical inheritance that lacks both content and relevance to the realities of the country and region today? The current happenings in Nigeria and most African countries such as the flagrant disregard of court orders by the Executive, indicate clearly that the concept constitutionalism ordinarily goes beyond mere form and strikes at the substance of a constitution. It, therefore, involves a consideration of whether there are provisions in the constitution which limit arbitrariness in the exercise of political powers by providing checks and balances upon such exercise. These questions underscore the need for Africa to craft its own understanding of the separation of powers between the arms of government in furtherance of good governance as it has been seen that it is possible to have a constitution in place which may just be a mere statement of unenforceable ‘rights’ or may be bereft of provisions guaranteeing liberty or adequate and necessary restraint on exercise of government. This paper seeks to expatiate on the importance of the nexus between constitutionalism and democratic process and a juxtaposition of practices between Nigeria and South Africa. The article notes that an abstract analysis of constitutionalism without recourse to the democratic process is meaningless and also analyses the structure of government of some selected African countries. These are examined the extent to which the doctrine operates within the arms of government and concludes that it should not just be regarded as a general constitutional principle but made rigid or perhaps effective and binding through law and institutional reforms.

Keywords: checks and balances, constitutionalism, democratic process, separation of power

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Authors: Muhammad Abid

Abstract:

The ultimate goal of this research was to produce a cold galvanizing compound (CGC) at reduced pigment volume concentration (PVC) to protect metallic structures from corrosion. The influence of the partial replacement of Zn dust by nano-layered graphene (NGr) and Zn metal nanoparticles on the electrochemical, morphological, rheological, and mechanical properties of CGC was investigated. EIS was used to explore the electrochemical nature of coatings. The EIS results revealed that the partial replacement of Zn by NGr and Zn nanoparticles enhanced the cathodic protection at reduced PVC (4:1) by improving the electrical contact between the Zn particles and the metal substrate. The Tafel scan was conducted to support the cathodic behaviour of the coatings. The sample formulated solely with Zn at PVC 4:1 was found to be dominated in physical barrier characteristics over cathodic protection. By increasing the concentration of NGr in the formulation, the corrosion potential shifted towards a more negative side. The coating with 1.5% NGr showed the highest galvanic action at reduced PVC. FE-SEM confirmed the interconnected network of conducting particles. The coating without NGr and Zn nanoparticles at PVC 4:1 showed significant gaps between the Zn dust particles. The novelty was evidenced when micrographs showed the consistent distribution of NGr and Zn nanoparticles all over the surface, which acted as a bridge between spherical Zn particles and provided cathodic protection at a reduced PVC. The layered structure of graphene also improved the physical shielding effect of the coatings, which limited the diffusion of electrolytes and corrosion products (oxides/hydroxides) into the coatings, which was reflected by the salt spray test. The rheological properties of coatings showed good liquid/fluid properties. All the coatings showed excellent adhesion but had different strength values. A real-time scratch resistance assessment showed all the coatings had good scratch resistance.

Keywords: protective coatings, anti-corrosion, galvanization, graphene, nanomaterials, polymers

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Authors: Muna Khethier Abbass, Bassma Finner Sultan

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In this research the effect of Al2O3 nanoparticles on corrosion behavior of aluminum base alloy(Al-4.5wt%Cu-1.5wt%Mg) has been investigated. Nanocomopsites reinforced with variable contents of 1,3 & 5wt% of Al2O3 nanoparticles were fabricated using powder metallurgy. All samples were prepared from the base alloy powders under the best powder metallurgy processing conditions of 6 hr of mixing time , 450 MPa of compaction pressure and 560°C of sintering temperature. Density and micro hardness measurements, and electrochemical corrosion tests are performed for all prepared samples in 3.5wt%NaCl solution at room temperature using potentiostate instrument. It has been found that density and micro hardness of the nanocomposite increase with increasing of wt% Al2O3 nanoparticles to Al matrix. It was found from Tafel extrapolation method that corrosion rates of the nanocomposites reinforced with alumina nanoparticles were lower than that of base alloy. From results of corrosion test by potentiodynamic cyclic polarization method, it was found the pitting corrosion resistance improves with adding of Al2O3 nanoparticles . It was noticed that the pits disappear and the hysteresis loop disappears also from anodic polarization curve.

Keywords: powder metallurgy, nano composites, Al-Cu-Mg alloy, electrochemical corrosion

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Authors: Z. V. P. Murthy, Preeti Arunachalam, Sangeeta Balram

Abstract:

Removal of metal ions from different wastewaters has become important due to their effects on living beings. Cadmium is one of the heavy metals found in different industrial wastewaters. There are many conventional methods available to remove heavy metals from wastewaters like adsorption, membrane separations, precipitation, electrolytic methods, etc. and all of them have their own advantages and disadvantages. The present work deals with the use of natural biosorbents (chitin and chitosan) to separate cadmium ions from aqueous solutions. The adsorption data were fitted with different isotherms and kinetics models. Amongst different adsorption isotherms used to fit the adsorption data, the Freundlich isotherm showed better fits for both the biosorbents. The kinetics data of adsorption of cadmium showed better fit with pseudo-second order model for both the biosorbents. Chitosan, the derivative from chitin, showed better performance than chitin. The separation results are encouraging.

Keywords: chitin, chitosan, cadmium, isotherm, kinetics

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Authors: Mahmoud A. Abdulhamid

Abstract:

Poly(ether-ether-ketone) (PEEK) has received increased attention due to its outstanding performance in different membrane applications including gas and liquid separation. However, it suffers from a semi-crystalline morphology, bad solubility and low porosity. To fabricate membranes from PEEK, the usage of harsh acid such as sulfuric acid is essential, regardless its hazardous properties. In this work, we report the molecular design of poly(ether-ether-ketones) (iPEEKs) with intrinsic porosity character, by incorporating kinked units into PEEK backbone such as spirobisindane, Tröger's base, and triptycene. The porous polymers were used to fabricate stable membranes for organic solvent nanofiltration application. To better understand the mechanism, we conducted molecular dynamics simulations to evaluate the possible interactions between the polymers and the solvents. Notable enhancement in separation performance was observed confirming the importance of molecular engineering of high-performance polymers. The iPEEKs demonstrated good solubility in polar aprotic solvents, a high surface area of 205–250 m² g⁻¹, and excellent thermal stability. Mechanically flexible nanofiltration membranes were prepared from N-methyl-2-pyrrolidone dope solution at iPEEK concentrations of 19–35 wt%. The molecular weight cutoff of the membranes was fine-tuned in the range of 450–845 g mol⁻¹ displaying 2–6 fold higher permeance (3.57–11.09 L m⁻² h⁻¹ bar⁻¹) than previous reports. The long-term stabilities were demonstrated by a 7 day continuous cross-flow filtration.

Keywords: molecular engineering, polymer synthesis, membrane fabrication, liquid separation

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Authors: El Hatka Hicham, Hafidi Youssef, Saghiri Khalid, Ittobane Najim

Abstract:

Flexible polyurethane foam (FPUF) is a low-density cellular material generally used as a cushioning material in many applications such as furniture, bedding, packaging, etc. It is commercially produced during a continuous process, where a reactive mixture of foam chemicals is poured onto a moving conveyor. FPUFs are produced by the catalytic balancing of two reactions involved, the blowing reaction (isocyanate-water) and the gelation reaction (isocyanate-polyol). The microstructure of FPUF is generally composed of soft phases (polyol phases) and rigid domains that separate into two domains of different sizes: the rigid polyurea microdomains and the macrodomains (larger aggregates). The morphological features of FPUF are strongly influenced by the phase separation morphology that plays a key role in determining the global FPUF properties. This phase-separated morphology results from a thermodynamic incompatibility between soft segments derived from aliphatic polyether and hard segments derived from the commonly used aromatic isocyanate. In order to improve the properties of FPUF against the different stresses faced by this material during its use, we report in this work a study of the phase separation phenomenon in FPUF that has been examined using SAXS WAXS and FTIR. Indeed, we have studied with these techniques the effect of water, isocyanates, and alkaline chlorides on the phase separation behavior. SAXS was used to study the morphology of the microphase separated, WAXS to examine the nature of the hard segment packing, and FTIR to investigate the hydrogen bonding characteristics of the materials studied. The prepared foams were shown to have different levels of urea phase connectivity; the increase in water content in the FPUF formulation leads to an increase in the amount of urea formed and consequently the increase of the size of urea aggregates formed. Alkali chlorides (NaCl, KCl, and LiCl) incorporated into FPUF formulations show that is the ability to prevent hydrogen bond formation and subsequently alter the rigid domains. FPUFs prepared by different isocyanate structures showed that urea aggregates are difficult to be formed in foams prepared by asymmetric diisocyanate, while are more easily formed in foams prepared by symmetric and aliphatic diisocyanate.

Keywords: flexible polyurethane foam, hard segments, phase separation, soft segments

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