Search results for: transition metal nitride coatings

Authors: Koyar Rane

Abstract:

Nano- to submicron size particles of narrow particle size distribution of semi-conducting TiO₂, ZnO, NiO, CuO, Fe₂O₃ have been synthesized by novel hydrazine method and tested for their gas sensing, photocatalytic and bactericidal activities and the behavior found to be enhanced when the oxides in the thin film forms, that obtained in a specially built spray pyrolysis reactor. Hydrazine method is novel in the sense, say, the UV absorption edge of the white pigment grade wide band gap (~3.2eV) TiO₂ and ZnO shifted to the visible region turning into yellowish particles, indicating modification occurring the band structure. The absorption in the visible region makes these oxides visible light sensitive photocatalysis in degrading pollutants, especially the organic dyes which otherwise increase the chemical oxygen demand of the drinking water, enabling the process feasible not under the harsh energetic UV radiation regime. The electromagnetic radiations on irradiation produce electron-hole pairs Semiconductor + hν → e⁻ + h⁺ The electron-hole pairs thus produced form Reactive Oxygen Species, ROS, on the surface of the semiconductors, O₂(adsorbed)+e⁻ → O₂• - superoxide ion OH-(surface)+h⁺ →•OH - Hydroxyl radical The ROS attack the organic material and micro-organisms. Our antibacterial studies indicate the metal oxides control the Biological Oxygen Demand (BOD) of drinking water which had beyond the safe level normally found in the municipal supply. Metal oxides in the thin film form show overall enhanced properties and the films are reusable. The results of the photodegradation and antibactericidal studies are discussed. Gas sensing studies too have been done to find the versatility of the multifunctional metal oxides.

Keywords: hydrazine method, visible light sensitive, photo-degradation of dyes, water/airborne pollutant

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Authors: K. Daoudi, Z. Othmen, S. El Helali, M.Oueslati, M. Oumezzine

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La0.7Sr0.3CoO3 thin films have been epitaxially grown on LaAlO3 and SrTiO3 (001) single-crystal substrates by metal organic deposition process. The structural and micro structural properties of the obtained films have been investigated by means of high resolution X-ray diffraction, Raman spectroscopy and transmission microscopy observations on cross-sections techniques. We noted a close dependence of the crystallinity on the used substrate and the film thickness. By increasing the annealing temperature to 1000ºC and the film thickness to 100 nm, the electrical resistivity was decreased by several orders of magnitude. The film resistivity reaches approximately 3~4 x10-4 Ω.cm in a wide interval of temperature 77-320 K, making this material a promising candidate for a variety of applications.

Keywords: cobaltite, thin films, epitaxial growth, MOD, TEM

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Authors: Sumit Kumar Das, Laishram Ladusingh

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Aim: The aim of the study is to examine the differential of epidemiological transition across fifteen agro-climatic zones of India and its effect on health-seeking behavior. Data and Methods: Unit level data on consumption expenditure on health of India from three decadal rounds conducted by National Sample Survey Organization are used for the analysis. These three rounds are 52nd (1995-96), 60th (2004-05) and 71st (2014-15). The age-adjusted prevalence rate for communicable diseases and non-communicable diseases are estimated for fifteen agro-climatic zones of India for three time periods. Bivariate analysis is used to find out determinants of health-seeking behavior. Multilevel logistic regression is used to examine factors effecting on household health-seeking behavior. Result: The prevalence of communicable diseases is increasing in most of the zones of India. Every South Indian zones, Gujarat plains, and lower Gangetic plain are facing the severe attack of dual burden of diseases. Demand for medical advice has increased in southern zones, and east zones, reliance on private healthcare facilities are increasing in most of the zone. Demographic characteristics of the household head have a significant impact on health-seeking behavior. Conclusion: Proper program implementation is required considering the disease prevalence and differential in the pattern of health seeking behavior. Along with initiation and strengthening of programs for non-communicable, existing programs for communicable diseases need to monitor and supervised strictly.

Keywords: agro-climatic zone, epidemiological transition, health-seeking behavior, multilevel regression

Procedia PDF Downloads 183

Authors: J. C. Colmenares, M. Paszkiewicz-Gawron, D. Lomot, S. R. Pradhan, A. Qayyum

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This work is a report of recent selected experiments of photocatalysis intensification using flow microphotoreactors (fabricated by an ultrasound-based technique) for photocatalytic selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (PhCHO) (in the frame of the concept of lignin valorization), and the proof of concept of intensifying a flow selective photocatalytic oxidation process by acoustic cavitation. The synthesized photocatalysts were characterized by using different techniques such as UV-Vis diffuse reflectance spectroscopy, X-ray diffraction, nitrogen sorption, thermal gravimetric analysis, and transmission electron microscopy. More specifically, the work will be on: a Design and development of metal-containing TiO₂ coated microflow reactor for photocatalytic partial oxidation of benzyl alcohol: The current work introduces an efficient ultrasound-based metal (Fe, Cu, Co)-containing TiO₂ deposition on the inner walls of a perfluoroalkoxy alkanes (PFA) microtube under mild conditions. The experiments were carried out using commercial TiO₂ and sol-gel synthesized TiO₂. The rough surface formed during sonication is the site for the deposition of these nanoparticles in the inner walls of the microtube. The photocatalytic activities of these semiconductor coated fluoropolymer based microreactors were evaluated for the selective oxidation of BnOH to PhCHO in the liquid flow phase. The analysis of the results showed that various features/parameters are crucial, and by tuning them, it is feasible to improve the conversion of benzyl alcohol and benzaldehyde selectivity. Among all the metal-containing TiO₂ samples, the 0.5 at% Fe/TiO₂ (both, iron and titanium, as cheap, safe, and abundant metals) photocatalyst exhibited the highest BnOH conversion under visible light (515 nm) in a microflow system. This could be explained by the higher crystallite size, high porosity, and flake-like morphology. b. Designing/fabricating photocatalysts by a sonochemical approach and testing them in the appropriate flow sonophotoreactor towards sustainable selective oxidation of key organic model compounds of lignin: Ultrasonication (US)-assitedprecipitaion and US-assitedhydrosolvothermal methods were used for the synthesis of metal-oxide-based and metal-free-carbon-based photocatalysts, respectively. Additionally, we report selected experiments of intensification of a flow photocatalytic selective oxidation through the use of ultrasonic waves. The effort of our research is focused on the utilization of flow sonophotocatalysis for the selective transformation of lignin-based model molecules by nanostructured metal oxides (e.g., TiO₂), and metal-free carbocatalysts. A plethora of parameters that affects the acoustic cavitation phenomena, and as a result the potential of sonication were investigated (e.g. ultrasound frequency and power). Various important photocatalytic parameters such as the wavelength and intensity of the irradiated light, photocatalyst loading, type of solvent, mixture of solvents, and solution pH were also optimized.

Keywords: heterogeneous photo-catalysis, metal-free carbonaceous materials, selective redox flow sonophotocatalysis, titanium dioxide

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Authors: Jae-Il Jeong, Hoon-Jae Park, Jung-Woo Cho, Yang-Gon Kim, Jin-Young Park, Joo-Young Oh, Si-Geun Choi, Seock-Sam Kim, Young Tae Cho, Chan Gyu Kim, Jong-Hyoung Kim

Abstract:

Bearing component has strongly required to decrease vibration and wear to achieve high durability and life time. In the industry field, bearing durability is improved by surface treatment on the bearing surface by centrifugal casting or gravity casting production method. However, this manufacturing method has caused problems such as long processing time, defect rate, and health harmful effect. To solve this problem, there is a laser cladding deposition treatment, which provides fast processing and food adhesion. Therefore, optimum conditions of white metal laser deposition should be studied to minimize bearing contact axis wear using laser cladding techniques. In this study, we deposit a soft white metal layer on SCM440, which is mainly used for shaft and bolt. On laser deposition process, the laser power and powder feed rate and laser head speed factors are controlled to find out the optimal conditions. We also measure hardness using micro Vickers, analyze FE-SEM (Field Emission Scanning Electron Microscope) and EDS (Energy Dispersive Spectroscopy) to study the mechanical properties and surface characteristics with various parameters change. Furthermore, this paper suggests the optimum condition of laser cladding deposition to apply in industrial fields. This work was supported by the Industrial Innovation Project of the Korea Evaluation Institute of Industrial Technology (KEIT) granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (Research no. 10051653).

Keywords: laser deposition, bearing, white metal, mechanical properties

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Authors: Yue Yan, Chang Nyung Kim

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The numerical investigation of the three-dimensional liquid-metal (LM) magnetohydrodynamic (MHD) flows in a curved duct with flow channel insert (FCI) is presented in this paper, based on the computational fluid dynamics (CFD) method. A uniform magnetic field is applied perpendicular to the duct. The interdependency of the flow variables is examined in terms of the flow velocity, current density, electric potential and pressure. The electromagnetic characteristics of the LM MHD flows are reviewed with an introduction of the electric-field component and electro-motive component of the current. The influence of the existence of the FCI on the fluid flow is investigated in detail. The case with FCI slit located near the side layer yields smaller pressure gradient with stable flow field.

Keywords: curved duct, flow channel insert, liquid-metal, magnetohydrodynamic

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Authors: Ji-yang Yu, Dan Huang, Guo-ping Feng, Xin Li, Lu-yuan Wang

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The navigation satellite network, especially the Beidou MEO Constellation, can relay data effectively with wide coverage and is applied in navigation, detection, and position widely. But the constellation has not been completed, and the amount of satellites on-board is not enough to cover the earth, which makes the data-relay disrupted or delayed in the transition process. The data-relay function needs to tolerant the delay or disruption in some extension, which make the Beidou MEO Constellation a delay/disruption-tolerant network (DTN). The traditional DTN designs mainly employ the relay table as the basic of data path schedule computing. But in practical application, especially in critical condition, such as the war-time or the infliction heavy losses on the constellation, parts of the nodes may become invalid, then the traditional DTN design could be useless. Furthermore, when transmitting the critical message in the navigation system, the maximum priority strategy is used, but the nodes still inquiry the relay table to design the path, which makes the delay more than minutes. Under this circumstances, it needs a function which could compute the optimum data path on-board in real-time according to the constellation states. The on-board critical message transmission design for navigation satellite delay/disruption-tolerant network (DTN) is proposed, according to the characteristics of navigation satellite network. With the real-time computation of parameters in the network link, the least-delay transition path is deduced to retransmit the critical message in urgent conditions. First, the DTN model for constellation is established based on the time-varying matrix (TVM) instead of the time-varying graph (TVG); then, the least transition delay data path is deduced with the parameters of the current node; at last, the critical message transits to the next best node. For the on-board real-time computing, the time delay and misjudges of constellation states in ground stations are eliminated, and the residual information channel for each node can be used flexibly. Compare with the minute’s delay of traditional DTN; the proposed transmits the critical message in seconds, which improves the re-transition efficiency. The hardware is implemented in FPGA based on the proposed model, and the tests prove the validity.

Keywords: critical message, DTN, navigation satellite, on-board, real-time

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Authors: T. Maruyama, T. Saida, S. Naritsuka, S. Iijima

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Single-walled carbon nanotubes (SWCNTs) are generally synthesized by chemical vapor deposition (CVD) using Fe, Co, and Ni as catalysts. However, due to the Ostwald ripening of metal catalysts, the diameter distribution of the grown SWCNTs is considerably wide (>2 nm), which is not suitable for electronics applications. In addition, reduction in the growth temperature is desirable for fabricating SWCNT devices compatible with the LSI process. Herein, we performed SWCNT growth by alcohol catalytic CVD using platinum-group metal catalysts (Pt, Rh, and Pd) because these metals have high melting points, and the reduction in the Ostwald ripening of catalyst particles is expected. Our results revealed that web-like SWCNTs were obtained from Pt and Rh catalysts at growth temperature between 500 °C and 600 °C by optimizing the ethanol pressure. The SWCNT yield from Pd catalysts was considerably low. By decreasing the growth temperature, the diameter and chirality distribution of SWCNTs from Pt and Rh catalysts became small and narrow. In particular, the diameters of most SWCNTs grown using Pt catalysts were below 1 nm and their diameter distribution was considerably narrow. On the contrary, SWCNTs can grow from Rh catalysts even at 300 °C by optimizing the growth condition, which is the lowest temperature recorded for SWCNT growth. Our results demonstrated that platinum-group metals are useful for the growth of small-diameter SWCNTs and facilitate low-temperature growth.

Keywords: carbon nanotube, chemical vapor deposition, catalyst, platinum, rhodium, palladium

Procedia PDF Downloads 347

Authors: Matthew E. Potter, Daniel J. Stewart, Lindsay M. Armstrong, Pier J. A. Sazio, Robert R. Raja

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Rising CO₂ levels in the atmosphere means that CO₂ is a highly desirable feedstock. This requires specific catalysts to be designed to activate this inert molecule, combining a catalytic site tailored for CO₂ transformations with a support that can readily adsorb CO₂. Metal organic frameworks (MOFs) are regularly used as CO₂ sorbents. The organic nature of the linker molecules, connecting the metal nodes, offers many post-synthesis modifications to introduce catalytic active sites into the frameworks. However, the metal nodes may be coordinatively unsaturated, allowing them to bind to organic moieties. Imidazoles have shown promise catalyzing the formation of cyclic carbonates from epoxides with CO₂. Typically, this synthesis route employs toxic reagents such as phosgene, liberating HCl. Therefore an alternative route with CO₂ is highly appealing. In this work we design active sites for CO₂ activation, by tethering substituted-imidazole organocatalytic species to the available Cr3+ metal nodes of a Cr-MIL-101 MOF, for the first time, to create a tailored species for carbon capture utilization applications. Our tailored design strategy combining a CO₂ sorbent, Cr-MIL-101, with an anchored imidazole results in a highly active and selective multifunctional catalyst, achieving turnover frequencies of over 750 hr-1. These findings demonstrate the synergy between the MOF framework and imidazoles for CO₂ utilization applications. Further, the effect of substrate variation has been explored yielding mechanistic insights into this process. Through characterization, we show that the structural and compositional integrity of the Cr-MIL-101 has been preserved on functionalizing the imidazoles. Further, we show the binding of the imidazoles to the Cr3+ metal nodes. This can be seen through our EPR study, where the distortion of the Cr3+ on binding to the imidazole shows the CO₂ binding site is close to the active imidazole. This has a synergistic effect, improving catalytic performance. We believe the combination of MOF support and organocatalyst allows many possibilities to generate new multifunctional catalysts for CO₂ utilisation. In conclusion, we have validated our design procedure, combining a known CO₂ sorbent, with an active imidazole species to create a unique tailored multifunctional catalyst for CO₂ utilization. This species achieves high activity and selectivity for the formation of cyclic carbonates and offers a sustainable alternative to traditional synthesis methods. This work represents a unique design strategy for CO₂ utilization while offering exciting possibilities for further work in characterization, computational modelling, and post-synthesis modification.

Keywords: carbonate, catalysis, MOF, utilisation

Procedia PDF Downloads 180

Authors: Yunpeng Xia, Jiajia Zha, Haoxin Huang, Hau Ping Chan, Chaoliang Tan

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Although the crystal phase of two-dimensional (2D) transition metal dichalcogenides (TMDs) has been proven to play an essential role in fabricating high-performance electronic devices in the past decade, its effect on the performance of 2D material-based flash memory devices still remains unclear. Here, we report the exploration of the effect of MoTe₂ in different phases as the charge trapping layer on the performance of 2D van der Waals (vdW) heterostructure-based flash memory devices, where the metallic 1T′-MoTe₂ or semiconducting 2H-MoTe₂ nanoflake is used as the floating gate. By conducting comprehensive measurements on the two kinds of vdW heterostructure-based devices, the memory device based on MoS2/h-BN/1T′-MoTe₂ presents much better performance, including a larger memory window, faster switching speed (100 ns) and higher extinction ratio (107), than that of the device based on MoS₂/h-BN/2H-MoTe₂ heterostructure. Moreover, the device based on MoS₂/h-BN/1T′-MoTe₂ heterostructure also shows a long cycle (>1200 cycles) and retention (>3000 s) stability. Our study clearly demonstrates that the crystal phase of 2D TMDs has a significant impact on the performance of nonvolatile flash memory devices based on 2D vdW heterostructures, which paves the way for the fabrication of future high-performance memory devices based on 2D materials.

Keywords: crystal Phase, 2D van der Waals heretostructure, flash memory device, floating gate

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Authors: Hadjer Didouh, Mohammed Hadj Melliani, Izzeddine Sameut Bouhaik

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Corrosion is a serious problem in industrial installations or metallic transport pipes. Corrosion is an interfacial process controlled by several parameters. The presence of microorganisms affects the kinetics of corrosion. This type of corrosion is often referred as bio-corrosion or corrosion influenced by microorganisms (MIC). The action of a microorganism or a bacterium is carried out by the formation of biofilm following its attachment to the metal surface. The formation of biofilm isolates the metal surface from its environment and allows the bacteria to control the parameters of the metal/bacteria interface. Biofilm formation by sulfate-reducing bacteria (SRB) X52 steel, poses substantial challenges in oil and gas industry SONATRACH of Algeria. This research delves into the complex attachment mechanisms employed by SRB biofilm on X52 carbon steel and investigates strategies for effective mitigation using biocides. The exploration commences by elucidating the underlying mechanisms facilitating SRB biofilm adhesion to X52 carbon steel, considering factors such as surface morphology, electrostatic interactions, and microbial extracellular substances. Advanced microscopy and spectroscopic techniques provide a support to the attachment processes, laying the foundation for targeted mitigation strategies. The use of 100 ppm of Moringa Oleifera extract biocide as a promising approach to control and prevent SRB biofilm formation on X52 carbon steel surfaces. Green extract undergo evaluation for their effectiveness in disrupting biofilm development while ensuring the integrity of the steel substrate. Systematic analysis is conducted on the biocide's impact on the biofilm's structural integrity, microbial viability, and overall attachment strength. This two-pronged investigation aims to deepen our comprehension of SRB biofilm dynamics and contribute to the development of effective strategies for mitigating its impact on X52 carbon steel.

Keywords: bio-corrosion, biofilm, attachement, metal/bacteria interface

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Authors: Johan Esbach

Abstract:

The entrepreneur has traditionally been defined through various historical lenses, emphasising individual traits, risk-taking, speculation, innovation and firm creation. However, these definitions often fail to address the dynamic nature of the modern entrepreneurial functions, which respond to unpredictable uncertainties and transition to routine management as certainty is achieved. This paper proposes a revised definition, positioning the entrepreneur as a dynamic function rather than a human construct, that emerges to address specific uncertainties in economic systems, but fades once uncertainty is resolved. By examining historical definitions and its limitations, including the works of Cantillon, Say, Schumpeter, and Knight, this paper identifies a gap in literature and develops a generalised definition for the entrepreneur. The revised definition challenges conventional thought by shifting focus from static attributes such as alertness, traits, firm creation, etc., to a dynamic role that includes reliability, adaptation, scalability, and adaptability. The methodology of this paper employs a mixed approach, combining theoretical analysis and case study examination to explore the dynamic nature of the entrepreneurial function in relation to uncertainty. The selection of case studies includes companies like Airbnb, Uber, Netflix, and Tesla, as these firms demonstrate a clear transition from entrepreneurial uncertainty to routine certainty. The data from the case studies is then analysed qualitatively, focusing on the patterns of entrepreneurial function across the selected companies. These results are then validated using quantitative analysis, derived from an independent survey. The primary finding of the paper will validate the entrepreneur as a dynamic function rather than a static, human-centric role. In considering the transition from uncertainty to certainty in companies like Airbnb, Uber, Netflix, and Tesla, the study shows that the entrepreneurial function emerges explicitly to address market, technological, or social uncertainties. Once these uncertainties are resolved and a certainty in the operating environment is established, the need for the entrepreneurial function ceases, giving way to routine management and business operations. The paper emphasises the need for a definitive model that responds to the temporal and contextualised nature of the entrepreneur. In adopting the revised definition, the entrepreneur is positioned to play a crucial role in the reduction of uncertainties within economic systems. Once the uncertainties are addressed, certainty is manifested in new combinations or new firms. Finally, the paper outlines policy implications for fostering environments that enables the entrepreneurial function and transition theory.

Keywords: dynamic function, uncertainty, revised definition, transition

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Authors: Michalina Aniola, Andrzej Katrusiak

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4,4-Bipyridine is an important compound often used in chemical practice and more recently frequently applied for designing new metal organic framework (MoFs). Here we present a systematic high-pressure study of its hydrobromide salt. 4,4-Bipyridine hydrobromide monohydrate, 44biPyHBrH₂O, at ambient-pressure is orthorhombic, space group P212121 (phase a). Its hydrostatic compression shows that it is stable to 1.32 GPa at least. However, the recrystallization above 0.55 GPa reveals a new hidden b-phase (monoclinic, P21/c). Moreover, when the 44biPyHBrH2O is heated to high temperature the chemical reactions of this compound in methanol solution can be observed. High-pressure experiments were performed using a Merrill-Bassett diamond-anvil cell (DAC), modified by mounting the anvils directly on the steel supports, and X-ray diffraction measurements were carried out on a KUMA and Excalibur diffractometer equipped with an EOS CCD detector. At elevated pressure, the crystal of 44biPyHBrH₂O exhibits several striking and unexpected features. No signs of instability of phase a were detected to 1.32 GPa, while phase b becomes stable at above 0.55 GPa, as evidenced by its recrystallizations. Phases a and b of 44biPyHBrH2O are partly isostructural: their unit-cell dimensions and the arrangement of ions and water molecules are similar. In phase b the HOH-Br- chains double the frequency of their zigzag motifs, compared to phase a, and the 44biPyH+ cations change their conformation. Like in all monosalts of 44biPy determined so far, in phase a the pyridine rings are twisted by about 30 degrees about bond C4-C4 and in phase b they assume energy-unfavorable planar conformation. Another unusual feature of 44biPyHBrH2O is that all unit-cell parameters become longer on the transition from phase a to phase b. Thus the volume drop on the transition to high-pressure phase b totally depends on the shear strain of the lattice. Higher temperature triggers chemical reactions of 44biPyHBrH2O with methanol. When the saturated methanol solution compound precipitated at 0.1 GPa and temperature of 423 K was required to dissolve all the sample, the subsequent slow recrystallization at isochoric conditions resulted in disalt 4,4-bipyridinium dibromide. For the 44biPyHBrH2O sample sealed in the DAC at 0.35 GPa, then dissolved at isochoric conditions at 473 K and recrystallized by slow controlled cooling, a reaction of N,N-dimethylation took place. It is characteristic that in both high-pressure reactions of 44biPyHBrH₂O the unsolvated disalt products were formed and that free base 44biPy and H₂O remained in the solution. The observed reactions indicate that high pressure destabilized ambient-pressure salts and favors new products. Further studies on pressure-induced reactions are carried out in order to better understand the structural preferences induced by pressure.

Keywords: conformation, high-pressure, negative area compressibility, polymorphism

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Authors: Xin Zhao. Xuerong Zheng. Andrey L. Rogach

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Using single metal atoms has been considered an efficient way to develop new HER and OER catalysts. MXenes, a class of two-dimensional materials, have attracted tremendous interest as promising substrates for single-atom metal catalysts. However, there is still a lack of systematic investigations on the interaction mechanisms between various MXenes substrates and single atoms. Besides, due to the poor interaction between metal atoms and substrates resulting in low loading and stability, dual-atom MXenes-based catalysts have not been successfully synthesized. We summarized the electrocatalytic enhancement mechanism of three MXenes-based single-atom catalysts through experimental and theoretical results demonstrating the stronger hybridization between Co 3d and surface-terminated O 2p orbitals, optimizing the electronic structure of Co single atoms in the composite. This, in turn, lowers the OER and HER energy barriers and accelerates the catalytic kinetics in the case of the Co@V2CTx composite. The poor interaction between single atoms and substrates can be improved by a surface modification to synthesize dual-atom catalysts. The synergistic electronic structure enhances the stability and electrocatalytic activity of the catalyst. Our study provides guidelines for designing single-atom and dual-atom MXene-based electrocatalysts and sheds light on the origins of the catalytic activity of single-atoms on MXene substrates.

Keywords: dual-atom catalyst, single-atom catalyst, MXene substrates, water splitting

Procedia PDF Downloads 69

Authors: Hadjer Didouh, Mohammed Hadj Melliani, Izzeddine Sameut Bouhaik

Abstract:

Corrosion is a serious problem in industrial installations or metallic transport pipes. Corrosion is an interfacial process controlled by several parameters. The presence of microorganisms affects the kinetics of corrosion. This type of corrosion is often referred to as bio-corrosion or corrosion influenced by microorganisms (MIC). The action of a microorganism or a bacterium is carried out by the formation of biofilm following its attachment to the metal surface. The formation of biofilm isolates the metal surface from its environment and allows the bacteria to control the parameters of the metal/bacteria interface. Biofilm formation by sulfate-reducing bacteria (SRB) X52 steel poses substantial challenges in the oil and gas industry SONATRACH of Algeria. This research delves into the complex attachment mechanisms employed by SRB biofilm on X52 carbon steel and investigates innovative strategies for effective mitigation using biocides. The exploration commences by elucidating the underlying mechanisms facilitating SRB biofilm adhesion to X52 carbon steel, considering factors such as surface morphology, electrostatic interactions, and microbial extracellular substances. Advanced microscopy and spectroscopic techniques provide support to the attachment processes, laying the foundation for targeted mitigation strategies. The use of 100 ppm of Moringa Oleifera extract biocide as a promising approach to control and prevent SRB biofilm formation on X52 carbon steel surfaces. Green extracts undergo evaluation for their effectiveness in disrupting biofilm development while ensuring the integrity of the steel substrate. Systematic analysis is conducted on the biocide's impact on the biofilm's structural integrity, microbial viability, and overall attachment strength. This two-pronged investigation aims to deepen our comprehension of SRB biofilm dynamics and contribute to the development of effective strategies for mitigating its impact on X52 carbon steel.

Keywords: attachment, bio-corrosion, biofilm, metal/bacteria interface

Procedia PDF Downloads 73

Authors: Maria Manzoor, Iram Gul, Muhammad Arshad

Abstract:

Bacterial strains were isolated from contaminated soil collected from Rawalpindi and Islamabad. The strains were investigated for lead resistance and their effect on Pb solubility and PGPR activity. Incubation experiments were carried for inoculated and unoculated soil containing different levels of Pb. Results revealed that few stains (BTM-4, BTM-11, BTM-14) were able to tolerate Pb up to 600 mg L-1, whereas five strains (BTM-3, BTM-6, BTM-10, BTM-21 and BTM-24) showed significant increase in solubility of Pb when compared to all other strains and control. The CaCl2 extractable Pb was increased by 13.6, 6.8, 4.4 and 2.4 folds compared to un-inoculated control soil at increased soil Pb concentration (500, 1000, 1500 and 200 mg kg-1, respectively). The selected bacterial strains (11) were further investigated for plant growth promotion activity through PGPR assays including. Germination and root elongation assays were also conducted under elevated metal concentration in controlled conditions to elucidate the effects of microbial strains upon plant growth and development. The results showed that all the strains tested in this study, produced significantly varying concentrations of IAA, siderophores and gibberellic acid along with ability to phosphorus solubilization index (PSI). The results of germination and root elongation assay further confirmed the beneficial role of the microbial strains in elevating metal stress through PGPR activity. Among all tested strains, BTM-10 significantly improved plant growth. 1.3 and 2.7 folds increase in root and shoot length was observed when compared to control. Which may be attributed to presence of important plant growth promoting enzymes (IAA 74.6 μg/ml; GA 19.23 μg/ml; Sidrophore units 49% and PSI 1.3 cm). The outcome of this study indicates that these Pb tolerant and solubilizing strains may have the potential for plant growth promotion under metal stress and can be used as mediator when coupled with heavy metal hyperaccumulator plants for phytoremediation of Pb contaminated soil.

Keywords: Pb resistant bacteria, Pb mobilizing bacteria, Phytoextraction of Pb, PGPR activity of bacteria

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Authors: Menglim Hoy, Suksun Horpibulsuk, Arul Arulrajah

Abstract:

The results of laboratory investigation of recycled asphalt pavement (RAP) – fly ash (FA) based geopolymer as a base material is presented in this paper. An alkaline activator, the mixture of NaOH and Na₂SiO₃, is used to synthesis RAP-FA based geopolymer. RAP-FA with water (RAP-FA blend) prepared as a control material. The strength develops and the strength against wet-dry was determined by the unconfined compression strength (UCS) test, then the microstructural properties were examined by scanning electron microscopy (SEM) and X-ray Diffraction (XRD) analysis. The toxicity characteristic leaching procedure (TCLP) test is conducted to measure its leachability of heavy metal. The results show both the RAP-FA blend and geopolymer can be used as a base course as its UCS values meet the minimum strength requirement specified by the Department of Highway, Thailand. The durability test results show the UCS of these materials increases with increasing the number of wet-dry cycles, reaching its peak at six wet-dry cycles. The XRD and SEM analyses indicate strength development of the RAP-FA blend occurs due to chemical reaction between a high Calcium in RAP with a high Silica and Alumina in FA led to producing calcium aluminate hydrate formation. The strength development of the RAP-FA geopolymer occurred resulted from the polymerization reaction. The TCLP results demonstrate there is no environmental risk of these stabilized materials. Furthermore, FA based geopolymer can reduce the leachability of heavy metal in the RAP-FA blend.

Keywords: recycled asphalt pavement, geopolymer, heavy metal, microstructure

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Authors: Aicha Bouhlala, Sabah Chettibi

Abstract:

A systematic investigation on structural, electronic, and magnetic properties of Ce₀.₇₅A₀.₂₅O₂ (A = W, Mo) is performed using first-principles calculations within the framework Full-Potential Linear Augmented Plane Wave (FP-LAPW) method based on the Density Functional Theory (DFT). The exchange-correlation potential has been treated using the generalized gradient approximation (WC-GGA) developed by Wu-Cohen. The host compound CeO2 was doped with transition metal atoms W and Mo in the doping concentration of 25% to replace the Ce atom. In structural properties, the equilibrium lattice constant is observed for the W-doped CeO₂ compound which exists within the value of 5.314 A° and the value of 5.317 A° for Mo-doped CeO2. The present results show that Ce₀.₇₅A₀.₂₅O₂ (A=W, Mo) systems exhibit semiconducting behavior in both spin channels. Although undoped CeO₂ is a non-magnetic semiconductor. The band structure of these doped compounds was plotted and they exhibit direct band gap at the Fermi level (EF) in the majority and minority spin channels. In the magnetic properties, the doped atoms W and Mo play a vital role in increasing the magnetic moments of the supercell and the values of the total magnetic moment are found to be 1.998 μB for Ce₀.₇₅W₀.₂₅O₂ and to be 2.002 μB for Ce₀.₇₅Mo₀.₂₅O₂ compounds. Calculated results indicate that the magneto-electronic properties of the Ce₁₋ₓAₓO₂(A= W, Mo) oxides supply a new way to the experimentalist for the potential applications in spintronics devices.

Keywords: FP-LAPW, DFT, CeO₂, properties

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Authors: Azhar Ulhaq, Zubair Yameen, Almas Anjum

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Frequency behaviour of self-excited induction generator (SEIG) wind turbines during control mode transition from grid connected to islanded mode is studied in detail. A robust control scheme for frequency regulation based on combined action of STATCOM, energy storage system (ESS) and pitch angle control for wind powered microgrid (MG) is proposed. Suggested STATCOM controller comprises a 3-phase voltage source converter (VSC) that contains insulated gate bipolar transistors (IGBTs) based pulse width modulation (PWM) inverters along with a capacitor bank. Energy storage system control consists of current controlled voltage source converter and battery bank. Both of them acting simultaneously after detection of island compensates for reactive and active power demands, thus regulating frequency at point of common coupling (PCC) and also improves load stability. STATCOM integrates at point of common coupling and ESS is connected to microgrids main bus. Results reveal that proposed control not only stabilizes frequency during transition duration but also minimizes sudden frequency imbalance caused by load variation or wind intermittencies in islanded operation. System is investigated with and without suggested control scheme. The efficacy of proposed strategy has been verified by simulation in MATLAB/Simulink.

Keywords: energy storage system, island, wind, STATCOM, self-excited induction generator, SEIG, transient

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Authors: Satya P. Dubey, Hrushikesh A Abhyankar, Veronica Marchante, James L. Brighton, Björn Bergmann

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Aims: To develop a mathematical model that simulates the ROP of PLA taking into account the effect of alternative energy to be implemented in a continuous reactive extrusion production process of PLA. Introduction: The production of large amount of waste is one of the major challenges at the present time, and polymers represent 70% of global waste. PLA has emerged as a promising polymer as it is compostable, biodegradable thermoplastic polymer made from renewable sources. However, the main limitation for the application of PLA is the traces of toxic metal catalyst in the final product. Thus, a safe and efficient production process needs to be developed to avoid the potential hazards and toxicity. It has been found that alternative energy sources (LASER, ultrasounds, microwaves) could be a prominent option to facilitate the ROP of PLA via continuous reactive extrusion. This process may result in complete extraction of the metal catalysts and facilitate less active organic catalysts. Methodology: Initial investigation were performed using the data available in literature for the reaction mechanism of ROP of PLA based on conventional metal catalyst stannous octoate. A mathematical model has been developed by considering significant parameters such as different initial concentration ratio of catalyst, co-catalyst and impurity. Effects of temperature variation and alternative energies have been implemented in the model. Results: The validation of the mathematical model has been made by using data from literature as well as actual experiments. Validation of the model including alternative energies is in progress based on experimental data for partners of the InnoREX project consortium. Conclusion: The model developed reproduces accurately the polymerisation reaction when applying alternative energy. Alternative energies have a great positive effect to increase the conversion and molecular weight of the PLA. This model could be very useful tool to complement Ludovic® software to predict the large scale production process when using reactive extrusion.

Keywords: polymer, poly-lactic acid (PLA), ring opening polymerization (ROP), metal-catalyst, bio-degradable, renewable source, alternative energy (AE)

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Authors: Dhritilekha Deka, Deepak Patwa, Ravi K., Archana M. Nair

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Bioaccumulation of heavy metal contaminants due to intense anthropogenic interference degrades the environment and ecosystem functions. Conventional physicochemical methods involve energy-intensive and costly methodologies. Phytoremediation, on the other hand, provides an efficient nature-based strategy for the reclamation of heavy metal-contaminated sites. However, the slow process and adaptation to high-concentration contaminant sequestration often limit the efficiency of the method. This necessitates natural amendments such as biochar to improve phytoextraction and stabilize the green cover. Biochar is a highly porous structure with high carbon sequestration potential and containing negatively charged functional groups that provide binding sites for the positively charged metals. This study aims to develop and determine the synergy between sugarcane bagasse biochar content and phytoremediation. A 60-day pot experiment using perennial tussock vetiver grass (Chrysopogon zizanioides) was conducted for different biochar contents of 1%, 2%, and 4% for the removal of cadmium and zinc. A concentration of 500 ppm is maintained for the amended and unamended control (CK) samples. The survival rates of the plants, biomass production, and leaf area index were measured for the plant growth characteristics. Results indicate a visible change in the plant growth and the heavy metal concentration with the biochar content. The bioconcentration factor (BCF) in the plant improved significantly for the 4% biochar content by 57% in comparison to the control CK treatment in Cd-treated soils. The Zn soils indicated the highest reduction in the metal concentration by 50% in the 2% amended samples and an increase in the BCF in all the amended samples. The translocation from the rhizosphere to the shoots was low but not dependent on the amendment content and varied for each contaminant type. The root-to-shoot ratio indicates higher values compared to the control samples. The enhanced tolerance capacities can be attributed to the nutrients released by the biochar in the soil. The study reveals the high potential of biochar as a phytoremediation amendment, but its effect is dependent on the soil and heavy metal and accumulator species.

Keywords: phytoextraction, biochar, heavy metals, chrysopogon zizanioides, bioaccumulation factor

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Authors: Cheng-Cao Sun, Shu-Jun Li, De-Jia Li

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Through analysis of a published micro-array-based high-throughput assessment, we discovered that miR-1275 was markedly down-regulated in nasopharyngeal carcinoma (NPC) tissues. However, little is known about its effect and mechanism involved in NPC development and progression. In this study, we investigated the role of miR-1275 on the development of NPC. The results indicated that miR-1275 was significantly down-regulated in primary NPC tissues, and very low levels were found in NPC cell lines. Ectopic expression of miR-1275 in NPC cell lines significantly suppressed cell growth as evidenced by cell viability assay and colony formation assay, through inhibition of HOXB5. In addition, miR-1275 suppresses G1/S transition through inhibition of HOXB5. Further, oncogene HOXB5 was revealed to be a putative target of miR-1275, which was inversely correlated with miR-1275 expression in NPC. Collectively, our study demonstrates that as a tumor suppressor, miR-1275 played a pivotal role on NPC through inhibiting cell proliferation, and suppressing G1/S transition by targeting oncogenic HOXB5.

Keywords: microRNA-1275 (miR-1275), HOXB5, nasopharyngeal carcinoma, proliferation

Procedia PDF Downloads 264

Authors: Aghaei Amirkhizi Navideh, Sadjadi Soodeh Sadat, Moghaddam Banaem Leila, Athari Allaf Mitra, Johari Daha Fariba

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Dendrimers are good candidates for preparing metal nanoparticles because they can structurally and chemically well-defined templates and robust stabilizers. Poly amidoamine (PAMAM) dendrimer-based multifunctional cancer therapeutic conjugates have been designed and synthesized in pharmaceutical industry. In addition, encapsulated nanoparticle surfaces are accessible to substrates so that catalytic reactions can be carried out. For preparation of dendimer-metal nanocomposite, a dendrimer solution containing an average of 55 Yb+3 ions per dendrimer was prepared. Prior to reduction, the pH of this solution was adjusted to 7.5 using NaOH. NaBH4 was used to reduce the dendrimer-encapsulated Yb+3 to the zerovalent metal. The pH of the resulting solution was then adjusted to 3, using HClO4, to decompose excess BH4-. The UV-Vis absorption spectra of the mixture were recorded to ensure the formation of Yb-G5-NH2 complex. High-resolution electron microscopy (HRTEM) and size distribution results provide additional information about dendimer-metal nanocomposite shape, size, and size distribution of the particles. The resulting mixture was irradiated in Tehran Research Reactor 2h and neutron fluxes were 3×1011 n/cm2.Sec and the specific activity was 7MBq. Radiochemical and chemical and radionuclide quality control testes were carried. Gamma Spectroscopy and High-performance Liquid Chromatography HPLC, Thin-Layer Chromatography TLC were recorded. The injection of resulting solution to solid tumor in mice shows that it could be resized the tumor. The studies about solid tumors and nano composites show that ytterbium encapsulated-dendrimer radiopharmaceutical could be introduced as a new therapeutic for the treatment of solid tumors.

Keywords: nano-radio pharmaceutical, ytterbium, PAMAM, dendrimers

Procedia PDF Downloads 503

Authors: Andrey Makarov

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This article will focus on the development of antitrust policy in transition economies in the context of preventing explicit and tacit collusion. Experience of BRICS, CIS (Ukraine, Kazakhstan) and CEE countries (Bulgaria, Hungary, Latvia, Lithuania, Poland, Romania, Slovakia, Slovenia, Czech Republic, Estonia) in the creation of antitrust institutions was analyzed, including both legislation and enforcement practice. Most of these countries in the early 90th were forced to develop completely new legislation in the field of protection of competition and it is important to compare different ways of building antitrust institutions and policy results. The article proposes a special approach to evaluation of preventing collusion mechanisms. This approach takes into account such enforcement problems as: classification problems (tacit vs explicit collusion, vertical vs horizontal agreements), flexibility of prohibitions (the balance between “per se” vs “rule of reason” approaches de jure and in practice), design of sanctions, private enforcement challenge, leniency program mechanisms, the role of antitrust authorities etc. The analysis is conducted using both official data, published by competition authorities, and expert assessments. The paper will show how the integration process within the EU predetermined some aspects of the development of antitrust policy in CEE countries, including the trend of the use of "rule of reason" approach. Simultaneously was analyzed the experience of CEE countries in special mechanisms of government intervention. CIS countries in the development of antitrust policy followed more or less original ways, without such a great impact from the European Union, more attention will be given to Russian experience in this field, including the analysis of judicial decisions in antitrust cases. Main problems and challenges for transition economies in this field will be shown, including: Legal uncertainty problem; Problem of rigidity of prohibitions; Enforcement priorities of the regulator; Interaction of administrative and criminal law, limited effectiveness of criminal sanctions in the antitrust field; The effectiveness of leniency program design; Private enforcement challenge.

Keywords: collusion, antitrust policy, leniency program, transition economies, Russia, CEE

Procedia PDF Downloads 446

Authors: Lotfi Khiari, Antoine Karam, Claude-Alla Joseph, Marc Hébert

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The main objective of incineration of sludge generated from municipal or agri-food waste treatment plant is to reduce the volume of sludge to be disposed of as a solid or liquid waste, whilst concentrating or destroying potentially harmful volatile substances. In some cities in Canada and United States of America (USA), a large amount of sludge is incinerated, which entails a loss of organic matter and water leading to phosphorus, potassium and some metallic trace element (MTE) accumulation in ashes. The purpose of this study was to evaluate the concentration of potentially hazardous MTE such as cadmium (Cd), lead (Pb) and mercury (Hg) in twelve sludge incineration ash samples obtained from municipal wastewater and other food processing waste treatments from Canada and USA. The average, maximum, and minimum values of MTE in ashes were calculated for each city individually and all together. The trace metal concentration values were compared to the literature reported values. The concentrations of MTE in ashes vary widely depending on the sludge origins and treatment options. The concentrations of MTE in ashes were found the range of 0.1-6.4 mg/kg for Cd; 13-286 mg/kg for Pb and 0.1-0.5 mg/kg for Hg. On average, the following order of metal concentration in ashes was observed: Pb > Cd > Hg. Results show that metal contents in most ashes were similar to MTE levels in synthetic inorganic fertilizers and many fertilizing residual materials. Consequently, the environmental effects of MTE content of these ashes would be low.

Keywords: biosolids, heavy metals, recycling, sewage sludge

Procedia PDF Downloads 380

Authors: A. Parra Parra, M. Vlasova, P. A. Marquez, M. Kakazey, M. C. Resendiz Gonzalez

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The work of water treatment plants from various sources of pollution includes a biological treatment stage using activated sludge. Due to the large volume of toxic activated sludge waste (WAS) generated and soil contamination during its storage, WAS disposal technologies are being continuously developed. The most common is the carbonization of WAS. The carbonization products are various forms of ordered and disordered carbon material having different reactivity. The aim of this work was to study the reduction process of Fe₂O₃ mixed with activated sludge waste (WAS). It could be assumed that the simultaneous action of the WAS thermal decomposition process, accompanied by the formation of reactive nano-carbon, with carbothermal reduction of the Fe₂O₃, will permit intensify reduction of metal oxide up to stage of metal and iron carbide formation. The studies showed that the temperature treatment in the region of (800-1000) °C for 1 hour under conditions of oxygen deficiency is accompanied by the occurrence of reactions: Fe₂O₃ → Fe₃O₄ → FeO → Fe, which are typical for the metallurgical process of iron smelting, but less energy-intensive. Depending on the ratio of the WAS - Fe₂O₃ components and the temperature-time regime of reduction of iron oxide, it is possible to distinguish the stages of the predominant formation of ferromagnetic compounds, cast iron, and iron carbide. The results indicated the promise of using WAS as a metals oxide reducing agent and obtaining of ceramic-based on metal carbides.

Keywords: carbothermal reduction, Fe₂O₃, FeₓOᵧ-C, waste activated sludge

Procedia PDF Downloads 134

Authors: Sourina Bej

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Since the process of decolonization in 1940, several countries in South Asia have witnessed intra-state conflicts owing to ineffective political governance. The conflicts have remained protracted as the countries have failed to make a holistic transition to a democratic state. Nepal is one such South Asian country facing a turmultous journey from monarchy to republicanism. The paper aims to focus on the democratic transition in the context of Nepal’s political, legal and economic institutions. The presence of autocratic feudalistic and centralised state structure with entrenched socio-economic inequalities has resulted in mass uprising only to see the country slip back to the old order. Even a violent civil war led by the Maoists could not overhaul the political relations or stabilize the democratic space. The paper aims to analyse the multiple political, institutional and operational challenges in the implementation of the peace agreement with the Maoist. Looking at the historical background, the paper will examine the problematic nation-building that lies at the heart of fragile peace process in Nepal. Regional dynamics have played a big role in convoluting the peace-building. The new constitution aimed at conflict resolution brought to the open, deep seated hatred among different ethnic groups in Nepal. Apart from studying the challenges to the peace process and the role of external players like India and China in the political reconstruction, the paper will debate on a viable federal solution to the ethnic conflict in Nepal. If the current government fails to pass a constitution accepted by most ethnic groups, Nepal will remain on the brink of new conflict outbreaks.

Keywords: democratisation, ethnic conflict, Nepal, peace process

Procedia PDF Downloads 277

Authors: Sarita Sindhu, Vinay Kumar

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The growing demand for efficient energy storage in applications such as portable electronics, electric vehicles, and renewable energy systems has emphasized the need for advanced energy storage materials. This study addresses the pressing need for efficient energy storage materials by exploring the synthesis and application of a composite of activated carbon (AC) and nickel sulfide (NiS) for supercapacitors. Activated carbon, possessing high surface area and excellent electrochemical stability, was combined with nickel sulfide, a transition metal sulfide with high theoretical capacitance, to enhance the electrochemical performance of the composite material. Characterization techniques, including scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR), were employed to analyze the morphology, crystalline structure, and bonding characteristics, confirming the successful formation of a uniformly distributed AC/NiS composite. Electrochemical evaluations revealed that the AC/NiS composite exhibited superior capacitance, excellent rate capability, and enhanced cycling stability compared to pure AC and NiS. The synergistic effect of the large surface area from activated carbon and redox-active sites of nickel sulfide provided an improved energy storage capacity, making this composite a promising electrode material for high-performance supercapacitors.

Keywords: activated carbon, energy storage, sulfide, surface area

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Authors: Y. Kalachyova, O. Lyutakov, V. Svorcik

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One of the most significant obstacles for the application of surface enhanced Raman spectroscopy (SERS) is the poor reproducibility of SERS active substrates: SERS intensity can be varied from one substrate to another and moreover along the one substrate surface. High enhancement of the near-field intensity is the key factor for ultrasensitive SERS realization. SERS substrate can be prepared through introduction of highly ordered metal array, where light focusing is achieved through excitation of surface plasmon-polaritons (SPPs). In this work, we report the preparation of silver nanostructures with plasmon absorption peaks tuned by the metal arrangement. Excimer laser modification of poly(methyl methacrylate) followed by silver evaporation is proposed as an effective way for the creation of reproducible and effective surface plasmon-polaritons (SPP)-based SERS substrate. Theoretical and experimental studies were performed to optimize structure parameter for effective SPP excitation. It was found that the narrow range of grating periodicity and metal thickness exist, where SPPs can be most efficiently excited. In spite of the fact, that SERS response was almost always achieved, the enhancement factor was found to vary more with the effectivity of SPP excitation. When the real structure parameters were set to optimal for SPP excitation, a SERS enhancement factor was achieved up to four times. Theoretical and experimental investigation of SPP excitation on the two-dimensional periodical silver array was performed with the aim to make SERS response as high as possible.

Keywords: grating, nanostructures, plasmon-polaritons, SERS

Procedia PDF Downloads 268

Authors: Tom Farrelly, Yvoonne Kavanagh, Tony Murphy

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In the last 20 years, Ireland has enjoyed an upsurge in the number of international students coming to avail of its well-regarded Higher Education system. While welcome, the influx of international students has posed a number of cultural, social and academic challenges for the Irish HE sector, both at institutional and individual lecturer level. Notwithstanding the challenge to the Irish HE sector, the difficulties that incoming students face needs to be acknowledged and addressed. For students who have never left their home country before the transition can be daunting even if they have not learned the customs and ways of the new country. In 2013, Ireland’s National Forum for the Advancement of Teaching and Learning in Higher Education invited submissions from interested parties to design and implement digital supports aimed at assisting students transitioning into or exiting higher education. Five colleges—the Institute of Technology, Tralee; University College Cork, Institute of Technology, Carlow; Cork Institute of Technology and Waterford Institute of Technology—collectively known as the Southern Cluster, were granted funding to research and develop digital objects to support international students' transition into the Irish higher education system. One of the key fundamentals of this project was its strong commitment to incorporating the student voice to help inform the design of the digital objects. The primary research method used to ascertain student views was the circulation of an online questionnaire using SurveyMonkey to existing international students in each of the five participant colleges. The questionnaire sought to examine the experiences and opinions of the students in relation to three main aspects of their living and studying in Ireland (hence the name of the project LiveAndLearnInIreland) (1) the academic environment (2) the social aspects of living in Ireland and (3) the practical aspects of living in Ireland. The response to the survey (n=573), revealed a number of sometimes surprising issues and themes for the digital objects to address. The research, therefore, offers insight into the types of concerns that any college, whether in Ireland or further afield, needs to take into consideration, if it is to genuinely assist what can be a difficult transition for the international student. That said, while there are a number of themes that emerged that have international implications there are other themes that have a particular resonance for the Irish HE sector.

Keywords: international, transition, support, inclusion

Procedia PDF Downloads 217