Search results for: metal loaded adsorption
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 3613

Search results for: metal loaded adsorption

2023 Mesocarbon Microbeads Modification of Stainless-Steel Current Collector to Stabilize Lithium Deposition and Improve the Electrochemical Performance of Anode Solid-State Lithium Hybrid Battery

Authors: Abebe Taye

Abstract:

The interest in enhancing the performance of all-solid-state batteries featuring lithium metal anodes as a potential alternative to traditional lithium-ion batteries has prompted exploration into new avenues. A promising strategy involves transforming lithium-ion batteries into hybrid configurations by integrating lithium-ion and lithium-metal solid-state components. This study is focused on achieving stable lithium deposition and advancing the electrochemical capabilities of solid-state lithium hybrid batteries with anodes by incorporating mesocarbon microbeads (MCMBs) blended with silver nanoparticles. To achieve this, mesocarbon microbeads (MCMBs) blended with silver nanoparticles are coated on stainless-steel current collectors. These samples undergo a battery of analyses employing diverse techniques. Surface morphology is studied through scanning electron microscopy (SEM). The electrochemical behavior of the coated samples is evaluated in both half-cell and full-cell setups utilizing an argyrodite-type sulfide electrolyte. The stability of MCMBs in the electrolyte is assessed using electrochemical impedance spectroscopy (EIS). Additional insights into the composition are gleaned through X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and energy-dispersive X-ray spectroscopy (EDS). At an ultra-low N/P ratio of 0.26, stability is upheld for over 100 charge/discharge cycles in half-cells. When applied in a full-cell configuration, the hybrid anode preserves 60.1% of its capacity after 80 cycles at 0.3 C under a low N/P ratio of 0.45. In sharp contrast, the capacity retention of the cell using untreated MCMBs declines to 20.2% after a mere 60 cycles. The introduction of mesocarbon microbeads (MCMBs) combined with silver nanoparticles into the hybrid anode of solid-state lithium batteries substantially elevates their stability and electrochemical performance. This approach ensures consistent lithium deposition and removal, mitigating dendrite growth and the accumulation of inactive lithium. The findings from this investigation hold significant value in elevating the reversibility and energy density of lithium-ion batteries, thereby making noteworthy contributions to the advancement of more efficient energy storage systems.

Keywords: MCMB, lithium metal, hybrid anode, silver nanoparticle, cycling stability

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2022 Assessment of the Physical and Chemical Characteristics of Ugbogui River, Edo State, Nigeria

Authors: Iyagbaye O. Rich, Omoigberale O. Michael, Iyagbaye A. Louis

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The physical, chemical parameters and some trace contents of Ugbogui in Edo State, Nigeria were investigated from August 2015 to April 2016. Four stations were studied from upstream to downstream using standard methods. A total of thirty-three (33) physical and chemical characteristics and trace metal contents were examined; Air and water temperatures, depth, transparency, colour, turbidity, flow velocity, pH, total alkalinity, conductivity and dissolved solids etc. Other includes dissolved oxygen, oxygen saturation, biochemical oxygen demand, chloride, phosphate, sodium, nitrate, sulphate, potassium, calcium, magnesium, iron, lead, copper, zinc, nickel, cadmium, vanadium and chromium. Eleven (11) parameters exhibited clear seasonal variations. However, there were high significant differences (p < 0.01) in the values of depth, colour, total suspended solid, biochemical oxygen demand, chemical oxygen demand, chloride, bicarbonate, phosphate, sulphate, iron, manganese, zinc, copper, chromium and cadmium among the stations. The anthropogenic activities had negatively impacted at station 3 of the river, although most of the recorded values were still within permissible limits.

Keywords: anthropogenic activities, Nigeria, permissible limits, physical and chemical parameters, trace metal, water quality

Procedia PDF Downloads 112
2021 Polypropylene Matrix Enriched With Silver Nanoparticles From Banana Peel Extract For Antimicrobial Control Of E. coli and S. epidermidis To Maintain Fresh Food

Authors: Michail Milas, Aikaterini Dafni Tegiou, Nickolas Rigopoulos, Eustathios Giaouris, Zaharias Loannou

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Nanotechnology, a relatively new scientific field, addresses the manipulation of nanoscale materials and devices, which are governed by unique properties, and is applied in a wide range of industries, including food packaging. The incorporation of nanoparticles into polymer matrices used for food packaging is a field that is highly researched today. One such combination is silver nanoparticles with polypropylene. In the present study, the synthesis of the silver nanoparticles was carried out by a natural method. In particular, a ripe banana peel extract was used. This method is superior to others as it stands out for its environmental friendliness, high efficiency and low-cost requirement. In particular, a 1.75 mM AgNO₃ silver nitrate solution was used, as well as a BPE concentration of 1.7% v/v, an incubation period of 48 hours at 70°C and a pH of 4.3 and after its preparation, the polypropylene films were soaked in it. For the PP films, random PP spheres were melted at 170-190°C into molds with 0.8cm diameter. This polymer was chosen as it is suitable for plastic parts and reusable plastic containers of various types that are intended to come into contact with food without compromising its quality and safety. The antimicrobial test against Escherichia coli DFSNB1 and Staphylococcus epidermidis DFSNB4 was performed on the films. It appeared that the films with silver nanoparticles had a reduction, at least 100 times, compared to those without silver nanoparticles, in both strains. The limit of detection is the lower limit of the vertical error lines in the presence of nanoparticles, which is 3.11. The main reasons that led to the adsorption of nanoparticles are the porous nature of polypropylene and the adsorption capacity of nanoparticles on the surface of the films due to hydrophobic-hydrophilic forces. The most significant parameters that contributed to the results of the experiment include the following: the stage of ripening of the banana during the preparation of the plant extract, the temperature and residence time of the nanoparticle solution in the oven, the residence time of the polypropylene films in the nanoparticle solution, the number of nanoparticles inoculated on the films and, finally, the time these stayed in the refrigerator so that they could dry and be ready for antimicrobial treatment.

Keywords: antimicrobial control, banana peel extract, E. coli, natural synthesis, microbe, plant extract, polypropylene films, S.epidermidis, silver nano, random pp

Procedia PDF Downloads 153
2020 Finite Element Modeling of Two-Phase Microstructure during Metal Cutting

Authors: Junior Nomani

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This paper presents a novel approach to modelling the metal cutting of duplex stainless steels, a two-phase alloy regarded as a difficult-to-machine material. Calculation and control of shear strain and stresses during cutting are essential to achievement of ideal cutting conditions. Too low or too high leads to higher required cutting force or excessive heat generation causing premature tool wear failure. A 2D finite element cutting model was created based on electron backscatter diffraction (EBSD) data imagery of duplex microstructure. A mesh was generated using ‘object-oriented’ software OOF2 version V2.1.11, converting microstructural images to quadrilateral elements. A virtual workpiece was created on ABAQUS modelling software where a rigid body toolpiece advanced towards workpiece simulating chip formation, generating serrated edge chip formation cutting. Model results found calculated stress strain contour plots correlated well with similar finite element models tied with austenite stainless steel alloys. Virtual chip form profile is also similar compared experimental frozen machining chip samples. The output model data provides new insight description of strain behavior of two phase material on how it transitions from workpiece into the chip.

Keywords: Duplex stainless steel, ABAQUS, OOF2, Chip formation

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2019 Metal-Semiconductor Transition in Ultra-Thin Titanium Oxynitride Films Deposited by ALD

Authors: Farzan Gity, Lida Ansari, Ian M. Povey, Roger E. Nagle, James C. Greer

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Titanium nitride (TiN) films have been widely used in variety of fields, due to its unique electrical, chemical, physical and mechanical properties, including low electrical resistivity, chemical stability, and high thermal conductivity. In microelectronic devices, thin continuous TiN films are commonly used as diffusion barrier and metal gate material. However, as the film thickness decreases below a few nanometers, electrical properties of the film alter considerably. In this study, the physical and electrical characteristics of 1.5nm to 22nm thin films deposited by Plasma-Enhanced Atomic Layer Deposition (PE-ALD) using Tetrakis(dimethylamino)titanium(IV), (TDMAT) chemistry and Ar/N2 plasma on 80nm SiO2 capped in-situ by 2nm Al2O3 are investigated. ALD technique allows uniformly-thick films at monolayer level in a highly controlled manner. The chemistry incorporates low level of oxygen into the TiN films forming titanium oxynitride (TiON). Thickness of the films is characterized by Transmission Electron Microscopy (TEM) which confirms the uniformity of the films. Surface morphology of the films is investigated by Atomic Force Microscopy (AFM) indicating sub-nanometer surface roughness. Hall measurements are performed to determine the parameters such as carrier mobility, type and concentration, as well as resistivity. The >5nm-thick films exhibit metallic behavior; however, we have observed that thin film resistivity is modulated significantly by film thickness such that there are more than 5 orders of magnitude increment in the sheet resistance at room temperature when comparing 5nm and 1.5nm films. Scattering effects at interfaces and grain boundaries could play a role in thickness-dependent resistivity in addition to quantum confinement effect that could occur at ultra-thin films: based on our measurements the carrier concentration is decreased from 1.5E22 1/cm3 to 5.5E17 1/cm3, while the mobility is increased from < 0.1 cm2/V.s to ~4 cm2/V.s for the 5nm and 1.5nm films, respectively. Also, measurements at different temperatures indicate that the resistivity is relatively constant for the 5nm film, while for the 1.5nm film more than 2 orders of magnitude reduction has been observed over the range of 220K to 400K. The activation energy of the 2.5nm and 1.5nm films is 30meV and 125meV, respectively, indicating that the TiON ultra-thin films are exhibiting semiconducting behaviour attributing this effect to a metal-semiconductor transition. By the same token, the contact is no longer Ohmic for the thinnest film (i.e., 1.5nm-thick film); hence, a modified lift-off process was developed to selectively deposit thicker films allowing us to perform electrical measurements with low contact resistance on the raised contact regions. Our atomic scale simulations based on molecular dynamic-generated amorphous TiON structures with low oxygen content confirm our experimental observations indicating highly n-type thin films.

Keywords: activation energy, ALD, metal-semiconductor transition, resistivity, titanium oxynitride, ultra-thin film

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2018 Generating Spherical Surface of Wear Drain in Cutting Metal by Finite Element Method Analysis

Authors: D. Kabeya Nahum, L. Y. Kabeya Mukeba

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In this work, the design of surface defects some support of the anchor rod ball joint. The future adhesion contact was rocking in manufacture machining, for giving by the numerical analysis of a short simple solution of thermo-mechanical coupled problem in process engineering. The analysis of geometrical evaluation and the quasi-static and dynamic states are discussed in kinematic dimensional tolerances onto surfaces of part. Geometric modeling using the finite element method (FEM) in rough part of such phase provides an opportunity to solve the nonlinearity behavior observed by empirical data to improve the discrete functional surfaces. The open question here is to obtain spherical geometry of drain wear with the operation of rolling. The formulation with (1 ± 0.01) mm thickness near the drain wear semi-finishing tool for studying different angles, do not help the professional factor in design cutting metal related vibration, friction and interface solid-solid of part and tool during this physical complex process, with multi-parameters no-defined in Sobolev Spaces. The stochastic approach of cracking, wear and fretting due to the cutting forces face boundary layers small dimensions thickness of the workpiece and the tool in the machining position is predicted neighbor to ‘Yakam Matrix’.

Keywords: FEM, geometry, part, simulation, spherical surface engineering, tool, workpiece

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2017 Removal of Vanadium from Industrial Effluents by Natural Ion Exchanger

Authors: Shashikant R. Kuchekar, Haribhau R. Aher, Priti M. Dhage

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The removal vanadium from aqueous solution using natural exchanger was investigated. The effects of pH, contact time and exchanger dose were studied at ambient temperature (25 0C ± 2 0C). The equilibrium process was described by the Langmuir isotherm model with adsorption capacity for vanadium. The natural exchanger i.e. tamarindus seeds powder was treated with formaldehyde and sulpuric acid to increase the adsorptivity of metals. The maximum exchange level was attained as 80.1% at pH 3 with exchanger dose 5 g and contact time 60 min. Method is applied for removal of vanadium from industrial effluents.

Keywords: industrial effluent, natural ion exchange, Tamarindous indica, vanadium

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2016 Experimental Studies on Fly Ash-Waste Sludge Mix Reinforced with Geofibres

Authors: Malik Shoeb Ahmad

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The aim of the present study is to carry out investigations on Class F fly ash obtained from NTPC thermal power plant, Dadri, U.P. (India) and electroplating waste sludge from Aligarh, U.P. (India) along with geofibre for its subsequent utilization in various geotechnical and highway engineering applications. The experimental studies such as California bearing ratio (CBR) tests were carried out to evaluate the strength of plain fly ash as well as fly ash-waste sludge mix reinforced with geofibre, as the CBR value is the vital parameters used in the design of flexible and rigid pavements. Results of the study show that the strength of the mix is highly dependent on the curing period and the sludge and geofibre content. The CBR values were determined for mix containing fly ash (83.5-93.5%), waste sludge (5-15%) and 1-2% geofibre. However, out of the various combinations of mixes the CBR value of the mix 88.5%FA+10%S+1.5%GF at 28 days of curing was found to be 53.52% when compared with the strength of plain fly ash. It has been observed that the fibre inclusion increases the strength of the plain fly ash and fly ash-waste sludge specimens by changing their brittle to ductile behavior. The TCLP leaching test was also conducted to determine the heavy metal concentration in the optimized mix. The results of TCLP test show that the heavy metal concentration in the mix 88.5%FA+10%S+1.5%G at 28 days of curing reduced substantially from 24 to 98% when compared with the concentration of heavy metals in the waste sludge collected from source. It has also been observed that the pH of the leachate of this mix is between 9-11, which ensures the proper stabilization of the heavy metals present in the mix. Hence, this study will certainly help in mass scale utilization of two industrial wastes viz., electroplating waste and fly ash, which are causing pollution to the environment to a great extent.

Keywords: Dadri fly ash, geofibre, electroplating waste sludge, CBR, TCLP

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2015 Process Optimization for 2205 Duplex Stainless Steel by Laser Metal Deposition

Authors: Siri Marthe Arbo, Afaf Saai, Sture Sørli, Mette Nedreberg

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This work aims to establish a reliable approach for optimizing a Laser Metal Deposition (LMD) process for a critical maritime component, based on the material properties and structural performance required by the maritime industry. The component of interest is a water jet impeller, for which specific requirements for material properties are defined. The developed approach is based on the assessment of the effects of LMD process parameters on microstructure and material performance of standard AM 2205 duplex stainless steel powder. Duplex stainless steel offers attractive properties for maritime applications, combining high strength, enhanced ductility and excellent corrosion resistance due to the specific amounts of ferrite and austenite. These properties are strongly affected by the microstructural characteristics in addition to microstructural defects such as porosity and welding defects, all strongly influenced by the chosen LMD process parameters. In this study, the influence of deposition speed and heat input was evaluated. First, the influences of deposition speed and heat input on the microstructure characteristics, including ferrite/austenite fraction, amount of porosity and welding defects, were evaluated. Then, the achieved mechanical properties were evaluated by standard testing methods, measuring the hardness, tensile strength and elongation, bending force and impact energy. The measured properties were compared to the requirements of the water jet impeller. The results show that the required amounts of ferrite and austenite can be achieved directly by the LMD process without post-weld heat treatments. No intermetallic phases were observed in the material produced by the investigated process parameters. A high deposition speed was found to reduce the ductility due to the formation of welding defects. An increased heat input was associated with reduced strength due to the coarsening of the ferrite/austenite microstructure. The microstructure characterizations and measured mechanical performance demonstrate the great potential of the LMD process and generate a valuable database for the optimization of the LMD process for duplex stainless steels.

Keywords: duplex stainless steel, laser metal deposition, process optimization, microstructure, mechanical properties

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2014 Desulphurization of Waste Tire Pyrolytic Oil (TPO) Using Photodegradation and Adsorption Techniques

Authors: Moshe Mello, Hilary Rutto, Tumisang Seodigeng

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The nature of tires makes them extremely challenging to recycle due to the available chemically cross-linked polymer and, therefore, they are neither fusible nor soluble and, consequently, cannot be remolded into other shapes without serious degradation. Open dumping of tires pollutes the soil, contaminates underground water and provides ideal breeding grounds for disease carrying vermins. The thermal decomposition of tires by pyrolysis produce char, gases and oil. The composition of oils derived from waste tires has common properties to commercial diesel fuel. The problem associated with the light oil derived from pyrolysis of waste tires is that it has a high sulfur content (> 1.0 wt.%) and therefore emits harmful sulfur oxide (SOx) gases to the atmosphere when combusted in diesel engines. Desulphurization of TPO is necessary due to the increasing stringent environmental regulations worldwide. Hydrodesulphurization (HDS) is the commonly practiced technique for the removal of sulfur species in liquid hydrocarbons. However, the HDS technique fails in the presence of complex sulfur species such as Dibenzothiopene (DBT) present in TPO. This study aims to investigate the viability of photodegradation (Photocatalytic oxidative desulphurization) and adsorptive desulphurization technologies for efficient removal of complex and non-complex sulfur species in TPO. This study focuses on optimizing the cleaning (removal of impurities and asphaltenes) process by varying process parameters; temperature, stirring speed, acid/oil ratio and time. The treated TPO will then be sent for vacuum distillation to attain the desired diesel like fuel. The effect of temperature, pressure and time will be determined for vacuum distillation of both raw TPO and the acid treated oil for comparison purposes. Polycyclic sulfides present in the distilled (diesel like) light oil will be oxidized dominantly to the corresponding sulfoxides and sulfone via a photo-catalyzed system using TiO2 as a catalyst and hydrogen peroxide as an oxidizing agent and finally acetonitrile will be used as an extraction solvent. Adsorptive desulphurization will be used to adsorb traces of sulfurous compounds which remained during photocatalytic desulphurization step. This desulphurization convoy is expected to give high desulphurization efficiency with reasonable oil recovery.

Keywords: adsorption, asphaltenes, photocatalytic oxidation, pyrolysis

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2013 Numerical Modelling and Experiment of a Composite Single-Lap Joint Reinforced by Multifunctional Thermoplastic Composite Fastener

Authors: Wenhao Li, Shijun Guo

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Carbon fibre reinforced composites are progressively replacing metal structures in modern civil aircraft. This is because composite materials have large potential of weight saving compared with metal. However, the achievement to date of weight saving in composite structure is far less than the theoretical potential due to many uncertainties in structural integrity and safety concern. Unlike the conventional metallic structure, composite components are bonded together along the joints where structural integrity is a major concern. To ensure the safety, metal fasteners are used to reinforce the composite bonded joints. One of the solutions for a significant weight saving of composite structure is to develop an effective technology of on-board Structural Health Monitoring (SHM) System. By monitoring the real-life stress status of composite structures during service, the safety margin set in the structure design can be reduced with confidence. It provides a means of safeguard to minimize the need for programmed inspections and allow for maintenance to be need-driven, rather than usage-driven. The aim of this paper is to develop smart composite joint. The key technology is a multifunctional thermoplastic composite fastener (MTCF). The MTCF will replace some of the existing metallic fasteners in the most concerned locations distributed over the aircraft composite structures to reinforce the joints and form an on-board SHM network system. Each of the MTCFs will work as a unit of the AU and AE technology. The proposed MTCF technology has been patented and developed by Prof. Guo in Cranfield University, UK in the past a few years. The manufactured MTCF has been successfully employed in the composite SLJ (Single-Lap Joint). In terms of the structure integrity, the hybrid SLJ reinforced by MTCF achieves 19.1% improvement in the ultimate failure strength in comparison to the bonded SLJ. By increasing the diameter or rearranging the lay-up sequence of MTCF, the hybrid SLJ reinforced by MTCF is able to achieve the equivalent ultimate strength as that reinforced by titanium fastener. The predicted ultimate strength in simulation is in good agreement with the test results. In terms of the structural health monitoring, a signal from the MTCF was measured well before the load of mechanical failure. This signal provides a warning of initial crack in the joint which could not be detected by the strain gauge until the final failure.

Keywords: composite single-lap joint, crack propagation, multifunctional composite fastener, structural health monitoring

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2012 Selective Extraction Separation of Vanadium and Chromium in the Leaching/Aqueous Solution with Trioctylamine

Authors: Xiaohua Jing

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Efficient extraction for separation of V and Cr in the leaching/aqueous solution is essential to the reuse of V and Cr in the V-Cr slag. Trioctylamine, a common tertiary amine extractant, with some good characters (e.g., weak base, insoluble in water and good stability) different from N1923, was investigated in this paper. The separation factor of Cr and V can be reached to 230.71 when initial pH of the aqueous solution is 0.5, so trioctylamine can be used for extracting Cr from the leaching/aqueous solution contained V and Cr. The highest extraction percentages of Cr and V were 98.73% and 90.22% when the initial pH values were 0.5 and 1.5, respectively. Via FT-IR spectra of loaded organic phase and trioctylamine, the hydrogen bond association mechanism of extracting V and Cr was investigated, which was the same with the way of extracting the two metals with primary amine N1923.

Keywords: selective extraction, trioctylamine, V and Cr, separation factor, hydrogen bond association

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2011 Microwave Assisted Solvent-free Catalytic Transesterification of Glycerol to Glycerol Carbonate

Authors: Wai Keng Teng, Gek Cheng Ngoh, Rozita Yusoff, Mohamed Kheireddine Aroua

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As a by-product of the biodiesel industries, glycerol has been vastly generated which surpasses the market demand. It is imperative to develop an efficient glycerol valorization processes in minimizing the net energy requirement and intensifying the biodiesel production. In this study, base-catalyzed transesterification of glycerol with dimethyl carbonate using microwave irradiation as heating method to produce glycerol carbonate was conducted by varing grades of glycerol i.e. 70%, 86% and 99% purity that obtained from biodiesel plant. Metal oxide catalysts were used with varying operating parameters including reaction time, DMC/glycerol molar ratio, catalyst weight %, temperature and stirring speed. From the study on the effect of different operating parameters; it was found that the type of catalyst used has the most significant effect on the transesterification reaction. Admist the metal oxide catalysts examined, CaO gave the best performance. This study indicates the feasibility of producing glycerol carbonate using different grade of glycerol in both conventional thermal activation and microwave irradiation with CaO as catalyst. Microwave assisted transesterification (MAT) of glycerol into glycerol carbonate has demostrated itself as an energy efficient route by achieving 94.3% yield of GC at 65°C, 5 minutes reaction time, 1 wt% CaO and DMC/glycerol molar ratio of 2. The advantages of MAT transesterification route has made the direct utilization of bioglycerol from biodiesel production without the need of purification. This has marked a more economical and less-energy intensive glycerol carbonate synthesis route.

Keywords: base-catalyzed transesterification, glycerol, glycerol carbonate, microwave irradiation

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2010 Design and Analysis of Crankshaft Using Al-Al2O3 Composite Material

Authors: Palanisamy Samyraj, Sriram Yogesh, Kishore Kumar, Vaishak Cibi

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The project is about design and analysis of crankshaft using Al-Al2O3 composite material. The project is mainly concentrated across two areas one is to design and analyze the composite material, and the other is to work on the practical model. Growing competition and the growing concern for the environment has forced the automobile manufactures to meet conflicting demands such as increased power and performance, lower fuel consumption, lower pollution emission and decrease noise and vibration. Metal matrix composites offer good properties for a number of automotive components. The work reports on studies on Al-Al2O3 as the possible alternative material for a crank shaft. These material have been considered for use in various components in engines due to the high amount of strength to weight ratio. These materials are significantly taken into account for their light weight, high strength, high specific modulus, low co-efficient of thermal expansion, good air resistance properties. In addition high specific stiffness, superior high temperature, mechanical properties and oxidation resistance of Al2O3 have developed some advanced materials that are Al-Al2O3 composites. Crankshafts are used in automobile industries. Crankshaft is connected to the connecting rod for the movement of the piston which is subjected to high stresses which cause the wear of the crankshaft. Hence using composite material in crankshaft gives good fuel efficiency, low manufacturing cost, less weight.

Keywords: metal matrix composites, Al-Al2O3, high specific modulus, strength to weight ratio

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2009 Preparation of Ni, Mg, and Fe Ions Doped Carbon-Based Catalyst with Ordered Mesoporous Configuration for Catalyzing the Production of Green Diesel from Fatty Acid and Waste Cooking Oil

Authors: Ya-Ting Liao, Chien-Chang Huang

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Green diesel is a renewable biofuel obtained from plant oil or fatty acid deoxygenation. Because the molecular structure of green diesel is similar to that of fossil fuel, green diesel can be directly used in present vehicle engines without blending with fossil fuel. In this study, mesoporous carbon-based catalysts with doped metal ions, such as Mg, Ni, or Fe, were prepared using co-polymers and gallic acid as molecular templates and carbon sources, respectively. The prepared catalysts were then applied to carry out the deoxygenation of fatty acid and waste cooking oil. To obtain the highest net energy from the produced green diesel, the catalyzed deoxygenation reaction and catalyst preparation processes were carried out under ambient conditions, respectively, to avoid using H₂ as a reagent and reducing agent. XRD, BET, SEM, EDS, FT-IR, and pyridine-IR characterized the composition and configuration of the prepared catalyst. The results display that the doped metal ions were well-dispersed in the carbon-based catalyst and the surface of the catalysts was rich in Lewis acid sites after the catalysts were calcined at the proper temperature. The pore size present on the catalyst was 9-11 nm. To catalyze the deoxygenation of fatty acid by the prepared catalysts at 320℃ under H₂-free conditions, high fatty acid conversion (99%) and high selectivity for hydrocarbons (78%) were obtained when the ratio of doped Ni to doped Mg was optimized.

Keywords: ordered mesoporous carbon, catalysts, hydrocarbons, deoxygenation

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2008 Steam Reforming of Acetic Acid over Microwave-Synthesized Ce0.75Zr0.25O2 Supported Ni Catalysts

Authors: Panumard Kaewmora, Thirasak Rirksomboon, Vissanu Meeyoo

Abstract:

Due to the globally growing demands of petroleum fuel and fossil fuels, the scarcity or even depletion of fossil fuel sources could be inevitable. Alternatively, the utilization of renewable sources, such as biomass, has become attractive to the community. Biomass can be converted into bio-oil by fast pyrolysis. In water phase of bio-oil, acetic acid which is one of its main components can be converted to hydrogen with high selectivity over effective catalysts in steam reforming process. Steam reforming of acetic acid as model compound has been intensively investigated for hydrogen production using various metal oxide supported nickel catalysts and yet they seem to be rapidly deactivated depending on the support utilized. A catalyst support such as Ce1-xZrxO2 mixed oxide was proposed for alleviating this problem with the anticipation of enhancing hydrogen yield. However, catalyst preparation methods play a significant role in catalytic activity and performance of the catalysts. In this work, Ce0.75Zr0.25O2 mixed oxide solid solution support was prepared by urea hydrolysis using microwave as heat source. After that nickel metal was incorporated at 15 wt% by incipient wetness impregnation method. The catalysts were characterized by several techniques including BET, XRD, H2-TPR, XRF, SEM, and TEM as well as tested for the steam reforming of acetic acid at various operating conditions. Preliminary results showed that a hydrogen yield of ca. 32% with a relatively high acetic conversion was attained at 650°C.

Keywords: acetic acid, steam reforming, microwave, nickel, ceria, zirconia

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2007 A Study on Kinetic of Nitrous Oxide Catalytic Decomposition over CuO/HZSM-5

Authors: Y. J. Song, Q. S. Xu, X. C. Wang, H. Wang, C. Q. Li

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The catalyst of copper oxide loaded on HZSM-5 was developed for nitrous oxide (N₂O) direct decomposition. The kinetic of nitrous oxide decomposition was studied for CuO/HZSM-5 catalyst prepared by incipient wetness impregnation method. The external and internal diffusion of catalytic reaction were considered in the investigation. Experiment results indicated that the external diffusion was basically eliminated when the reaction gas mixture gas hourly space velocity (GHSV) was higher than 9000h⁻¹ and the influence of the internal diffusion was negligible when the particle size of the catalyst CuO/HZSM-5 was small than 40-60 mesh. The experiment results showed that the kinetic of catalytic decomposition of N₂O was a first-order reaction and the activation energy and the pre-factor of the kinetic equation were 115.15kJ/mol and of 1.6×109, respectively.

Keywords: catalytic decomposition, CuO/HZSM-5, kinetic, nitrous oxide

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2006 Insights on Nitric Oxide Interaction with Phytohormones in Rice Root System Response to Metal Stress

Authors: Piacentini Diego, Della Rovere Federica, Fattorini Laura, Lanni Francesca, Cittadini Martina, Altamura Maria Maddalena, Falasca Giuseppina

Abstract:

Plants have evolved sophisticated mechanisms to cope with environmental cues. Changes in intracellular content and distribution of phytohormones, such as the auxin indole-3-acetic acid (IAA), have been involved in morphogenic adaptation to environmental stresses. In addition to phytohormones, plants can rely on a plethora of small signal molecules able to promptly sense and transduce the stress signals, resulting in morpho/physiological responses thanks also to their capacity to modulate the levels/distribution/reception of most hormones. Among these signaling molecules, nitrogen monoxide (nitric oxide – NO) is a critical component in several plant acclimation strategies to both biotic and abiotic stresses. Depending on its levels, NO increases plant adaptation by enhancing the enzymatic or non-enzymatic antioxidant systems or by acting as a direct scavenger of reactive oxygen/nitrogen (ROS/RNS) species produced during the stress. In addition, exogenous applications of NO-specific donor compounds showed the involvement of the signal molecule in auxin metabolism, transport, and signaling, under both physiological and stress conditions. However, the complex mechanisms underlying NO action in interacting with phytohormones, such as auxins, during metal stress responses are still poorly understood and need to be better investigated. Emphasis must be placed on the response of the root system since it is the first plant organ system to be exposed to metal soil pollution. The monocot Oryza sativa L. (rice) has been chosen given its importance as a stable food for some 4 billion people worldwide. In addition, increasing evidence has shown that rice is often grown in contaminated paddy soils with high levels of heavy metal cadmium (Cd) and metalloid arsenic (As). The facility through which these metals are taken up by rice roots and transported to the aerial organs up to the edible caryopses makes rice one of the most relevant sources of these pollutants for humans. This study aimed to evaluate if NO has a mitigatory activity in the roots of rice seedlings against Cd or As toxicity and to understand if this activity requires interactions with auxin. Our results show that exogenous treatments with the NO-donor SNP alleviate the stress induced by Cd, but not by As, in in-vitro-grown rice seedlings through increased intracellular root NO levels. The damages induced by the pollutants include root growth inhibition, root histological alterations and ROS (H2O2, O2●ˉ), and RNS (ONOOˉ) production. Also, SNP treatments mitigate both the root increase in root IAA levels and the IAA alteration in distribution monitored by the OsDR5::GUS system due to the toxic metal exposure. Notably, the SNP-induced mitigation of the IAA homeostasis altered by the pollutants does not involve changes in the expression of OsYUCCA1 and ASA2 IAA-biosynthetic genes. Taken together, the results highlight a mitigating role of NO in the rice root system, which is pollutant-specific, and involves the interaction of the signal molecule with both IAA and brassinosteroids at different (i.e., transport, levels, distribution) and multiple levels (i.e., transcriptional/post-translational levels). The research is supported by Progetti Ateneo Sapienza University of Rome, grant number: RG120172B773D1FF

Keywords: arsenic, auxin, cadmium, nitric oxide, rice, root system

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2005 Criminal Liability for Criminal Tax

Authors: Theresia Simatupang dan Rahmayanti

Abstract:

Tax Law is a legal product and therefore should be subject to the legal norms, both about this actions, implementation, and about the material. Law has always aimed at providing justice, and besides that the law as a tool used to organize the order or rule of law. tax classification of a crime in this is very necessary, because the crime of taxation is very detrimental to the country and is still very high in society and socialization associated with punishment in sentencing that would have to provide a deterrent for the perpetrators, so refer to the this, these criminal offenses can endanger the stability of the nation's economy and the country that require special snacks. The application of legal sanctions against the perpetrators of the crime of taxation already has a strong legal basis, namely UU KUP. UU KUP have loaded threat (sanctions) severe punishment for tax payers who commit offenses and crimes in the field of taxation, which is contained in Article 38, and Article 39, Article 41, Article 41 A, and 41 B as well as Article 43 of Law and Law No. 12 KUP about 1985 Land Tax and Building. Criminal sanctions against violators of the tax provision are important because tax payers sanctions for violating tax laws.

Keywords: accountability, tax crime, criminal liability, taxation

Procedia PDF Downloads 331
2004 Controlled Doping of Graphene Monolayer

Authors: Vedanki Khandenwal, Pawan Srivastava, Kartick Tarafder, Subhasis Ghosh

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We present here the experimental realization of controlled doping of graphene monolayers through charge transfer by trapping selected organic molecules between the graphene layer and underlying substrates. This charge transfer between graphene and trapped molecule leads to controlled n-type or p-type doping in monolayer graphene (MLG), depending on whether the trapped molecule acts as an electron donor or an electron acceptor. Doping controllability has been validated by a shift in corresponding Raman peak positions and a shift in Dirac points. In the transfer characteristics of field effect transistors, a significant shift of Dirac point towards positive or negative gate voltage region provides the signature of p-type or n-type doping of graphene, respectively, as a result of the charge transfer between graphene and the organic molecules trapped within it. In order to facilitate the charge transfer interaction, it is crucial for the trapped molecules to be situated in close proximity to the graphene surface, as demonstrated by findings in Raman and infrared spectroscopies. However, the mechanism responsible for this charge transfer interaction has remained unclear at the microscopic level. Generally, it is accepted that the dipole moment of adsorbed molecules plays a crucial role in determining the charge-transfer interaction between molecules and graphene. However, our findings clearly illustrate that the doping effect primarily depends on the reactivity of the constituent atoms in the adsorbed molecules rather than just their dipole moment. This has been illustrated by trapping various molecules at the graphene−substrate interface. Dopant molecules such as acetone (containing highly reactive oxygen atoms) promote adsorption across the entire graphene surface. In contrast, molecules with less reactive atoms, such as acetonitrile, tend to adsorb at the edges due to the presence of reactive dangling bonds. In the case of low-dipole moment molecules like toluene, there is a lack of substantial adsorption anywhere on the graphene surface. Observation of (i) the emergence of the Raman D peak exclusively at the edges for trapped molecules without reactive atoms and throughout the entire basal plane for those with reactive atoms, and (ii) variations in the density of attached molecules (with and without reactive atoms) to graphene with their respective dipole moments provides compelling evidence to support our claim. Additionally, these observations were supported by first principle density functional calculations.

Keywords: graphene, doping, charge transfer, liquid phase exfoliation

Procedia PDF Downloads 48
2003 Controlled Growth of Charge Transfer Complex Nanowire by Physical Vapor Deposition Method Using Dielectrophoretic Force

Authors: Rabaya Basori, Arup K. Raychaudhuri

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In recent years, a variety of semiconductor nanowires (NWs) has been synthesized and used as basic building blocks for the development of electronic and optoelectronic nanodevices. Dielectrophoresis (DEP) has been widely investigated as a scalable technique to trap and manipulate polarizable objects. This includes biological cells, nanoparticles, DNA molecules, organic or inorganic NWs and proteins using electric field gradients. In this article, we have used DEP force to localize nanowire growth by physical vapor deposition (PVD) method as well as control of NW diameter on field assisted growth of the NWs of CuTCNQ (Cu-tetracyanoquinodimethane); a metal-organic charge transfer complex material which is well known of resistive switching. We report a versatile analysis platform, based on a set of nanogap electrodes, for the controlled growth of nanowire. Non-uniform electric field and dielectrophoretic force is created in between two metal electrodes, patterned by electron beam lithography process. Suspended CuTCNQ nanowires have been grown laterally between two electrodes in the vicinity of electric field and dielectric force by applying external bias. Growth and diameter dependence of the nanowires on external bias has been investigated in the framework of these two forces by COMSOL Multiphysics simulation. This report will help successful in-situ nanodevice fabrication with constrained number of NW and diameter without any post treatment.

Keywords: nanowire, dielectrophoretic force, confined growth, controlled diameter, comsol multiphysics simulation

Procedia PDF Downloads 171
2002 Co-pyrolysis of Sludge and Kaolin/Zeolite to Stabilize Heavy Metals

Authors: Qian Li, Zhaoping Zhong

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Sewage sludge, a typical solid waste, has inevitably been produced in enormous quantities in China. Still worse, the amount of sewage sludge produced has been increasing due to rapid economic development and urbanization. Compared to the conventional method to treat sewage sludge, pyrolysis has been considered an economic and ecological technology because it can significantly reduce the sludge volume, completely kill pathogens, and produce valuable solid, gas, and liquid products. However, the large-scale utilization of sludge biochar has been limited due to the considerable risk posed by heavy metals in the sludge. Heavy metals enriched in pyrolytic biochar could be divided into exchangeable, reducible, oxidizable, and residual forms. The residual form of heavy metals is the most stable and cannot be used by organisms. Kaolin and zeolite are environmentally friendly inorganic minerals with a high surface area and heat resistance characteristics. So, they exhibit the enormous potential to immobilize heavy metals. In order to reduce the risk of leaching heavy metals in the pyrolysis biochar, this study pyrolyzed sewage sludge mixed with kaolin/zeolite in a small rotary kiln. The influences of additives and pyrolysis temperature on the leaching concentration and morphological transformation of heavy metals in pyrolysis biochar were investigated. The potential mechanism of stabilizing heavy metals in the co-pyrolysis of sludge blended with kaolin/zeolite was explained by scanning electron microscopy, X-ray diffraction, and specific surface area and porosity analysis. The European Community Bureau of Reference sequential extraction procedure has been applied to analyze the forms of heavy metals in sludge and pyrolysis biochar. All the concentrations of heavy metals were examined by flame atomic absorption spectrophotometry. Compared with the proportions of heavy metals associated with the F4 fraction in pyrolytic carbon prepared without additional agents, those in carbon obtained by co-pyrolysis of sludge and kaolin/zeolite increased. Increasing the additive dosage could improve the proportions of the stable fraction of various heavy metals in biochar. Kaolin exhibited a better effect on stabilizing heavy metals than zeolite. Aluminosilicate additives with excellent adsorption performance could capture more released heavy metals during sludge pyrolysis. Then heavy metal ions would react with the oxygen ions of additives to form silicate and aluminate, causing the conversion of heavy metals from unstable fractions (sulfate, chloride, etc.) to stable fractions (silicate, aluminate, etc.). This study reveals that the efficiency of stabilizing heavy metals depends on the formation of stable mineral compounds containing heavy metals in pyrolysis biochar.

Keywords: co-pyrolysis, heavy metals, immobilization mechanism, sewage sludge

Procedia PDF Downloads 55
2001 Crushing Analysis of Foam-Filled Thin-Walled Aluminum Profiles Subjected to Axial Loading

Authors: Michał Rogala, Jakub Gajewski

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As the automotive industry develops, passive safety is becoming an increasingly important aspect when designing motor vehicles. A commonly used solution is energy absorption by thin-walled construction. One such structure is a closed thin-walled profile fixed to the vehicle stringers. The article presents numerical tests of conical thin-walled profiles filled with aluminum foam. The columns were loaded axially with constant energy. On the basis of the results obtained, efficiency indicators were calculated. The efficiency of the foam filling was evaluated. Artificial neural networks were used for data analysis. The application of regression analysis was used as a tool to study the relationship between the quantities characteristic of the dynamic crush.

Keywords: aluminium foam, crashworthiness, neural networks, thin-walled structure

Procedia PDF Downloads 131
2000 Water Quality Assessment of Deep Wells in Western Misamis Oriental, Philippines

Authors: Girlie D. Leopoldo, Myrna S. Ceniza, Ronnie L. Besagas, Antonio Y. Asoy, Noel T. Dael, Romeo M. Del Rosario

Abstract:

The quality of groundwater from main deep well sources of seven (7) municipalities in Western Misamis Oriental, Philippines was examined. The study looks at the well waters’ physicochemical properties (temperture, pH, turbidity, conductivity, TDS, salinity, chlorides, TOC, and total hardness), the heavy metals and other metals (Pb, Cd, Al, As, Hg, Sb, Zn, Cu, Fe) and their microbiological (total coliform and E. coli) characteristics. The physicochemical properties of groundwater samples were found to be within the Philippine National Standards for Drinking Water (PNSDW)/US-EPA except for the TDS, chlorides, and hardness of some sources. Well waters from both Initao and Gitagum municipalities have TDS values of 643.2 mg/L and 578.4 mg/L, respectively, as compared to PNSDW/US-EPA standard limit of 500 mg/L. These same two municipalities Initao and Gitagum as well as the municipality of Libertad also have chloride levels beyond the 250 mg/L limit of PNSDW/US-EPA/EU with values at 360, 318 and 277 mg/L respectively. The Libertad sample also registered a total hardness of 407.5 mg/L CaCO3 as compared to the 300 mg/L PNSDW limit. These mentioned three (3) municipalities are noticed to have similar geologic structures. Although metal analyses revealed the presence of Zn, Cu and Fe in almost all well water sources, their concentrations are below allowable limit. All well waters from the seven municipalities failed in total coliform count. Escherichia coli were also found in well waters from four (4) municipalities including Laguindingan, Lugait, Gitagum, and Libertad. The presence of these pathogens in the well waters needs to be addressed to make the waters suitable for human consumption.

Keywords: groundwater, deep well, physico-chemical, heavy metal, microbiological

Procedia PDF Downloads 569
1999 Evaluation of Toxic Metals in Water Hyacinth (Eichhornia crassipes) from Valsequillo Reservoir, Puebla, Central Mexico

Authors: Jacobo Tabla, P. F. Rodriguez-Espinosa, M. E. Perez-Lopez

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Valsequillo reservoir located in Puebla City, Central Mexico receives water from the Atoyac River (Northwest) and from Alseseca River in the north. It has been the receptacle of municipal and industrial wastes for the past few decades affecting the water quality lethally. As a result, there is an outburst of water hyacinths (Eichhornia crassipes) in the reservoir occupying around 50 % of the total area. Therefore, the aim of the present work was to assess the concentration levels of toxic metals (Co, Zn, Ni, Cu and As) in the water hyacinths and the ambient waters during the dry season. Fourteen water samples and three water hyacinth samples were procured from the Valsequillo reservoir. The collected samples of water hyacinth (roots, rhizome, stems and leaves) were analyzed using an Inductively coupled plasma mass spectrometry (ICP-MS) Ultramass 700 (Varian Inc.) to determine the metal levels. Results showed that water hyacinth presented an exhaustion in metal capture from the inlet to outlet of the reservoir. The maximum bioaccumulation factors (BF) of Co, Zn, Ni, Cu and As were 5000, 47474, 4929, 17090 and 74000 respectively. On the other hand, the maximum Translocation Factor (TF) of 0.85 was observed in Zn, whilst Co presented the minimum TF of 0.059. Thus, the results presented the fact that water hyacinth in Valsequillo reservoir proves to be an important environmental utility for efficiently accumulating and translocating heavy metals from the ambient waters to its organelles (stems and leaves).

Keywords: bioaccumulation factor, toxic metals, translocation factor, water hyacinth

Procedia PDF Downloads 239
1998 Synthesis of Methanol through Photocatalytic Conversion of CO₂: A Green Chemistry Approach

Authors: Sankha Chakrabortty, Biswajit Ruj, Parimal Pal

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Methanol is one of the most important chemical products and intermediates. It can be used as a solvent, intermediate or raw material for a number of higher valued products, fuels or additives. From the last one decay, the total global demand of methanol has increased drastically which forces the scientists to produce a large amount of methanol from a renewable source to meet the global demand with a sustainable way. Different types of non-renewable based raw materials have been used for the synthesis of methanol on a large scale which makes the process unsustainable. In this circumstances, photocatalytic conversion of CO₂ into methanol under solar/UV excitation becomes a viable approach to give a sustainable production approach which not only meets the environmental crisis by recycling CO₂ to fuels but also reduces CO₂ amount from the atmosphere. Development of such sustainable production approach for CO₂ conversion into methanol still remains a major challenge in the current research comparing with conventional energy expensive processes. In this backdrop, the development of environmentally friendly materials, like photocatalyst has taken a great perspective for methanol synthesis. Scientists in this field are always concerned about finding an improved photocatalyst to enhance the photocatalytic performance. Graphene-based hybrid and composite materials with improved properties could be a better nanomaterial for the selective conversion of CO₂ to methanol under visible light (solar energy) or UV light. The present invention relates to synthesis an improved heterogeneous graphene-based photocatalyst with improved catalytic activity and surface area. Graphene with enhanced surface area is used as coupled material of copper-loaded titanium oxide to improve the electron capture and transport properties which substantially increase the photoinduced charge transfer and extend the lifetime of photogenerated charge carriers. A fast reduction method through H₂ purging has been adopted to synthesis improved graphene whereas ultrasonication based sol-gel method has been applied for the preparation of graphene coupled copper loaded titanium oxide with some enhanced properties. Prepared photocatalysts were exhaustively characterized using different characterization techniques. Effects of catalyst dose, CO₂ flow rate, reaction temperature and stirring time on the efficacy of the system in terms of methanol yield and productivity have been studied in the present study. The study shown that the newly synthesized photocatalyst with an enhanced surface resulting in a sustained productivity and yield of methanol 0.14 g/Lh, and 0.04 g/gcat respectively, after 3 h of illumination under UV (250W) at an optimum catalyst dosage of 10 g/L having 1:2:3 (Graphene: TiO₂: Cu) weight ratio.

Keywords: renewable energy, CO₂ capture, photocatalytic conversion, methanol

Procedia PDF Downloads 92
1997 Comparison of Methods for the Synthesis of Eu+++, Tb+++, and Tm+++ Doped Y2O3 Nanophosphors by Sol-Gel and Hydrothermal Methods for Bioconjugation

Authors: Ravindra P. Singh, Drupad Ram, Dinesh K. Gupta

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Rare earth ions doped metal oxides are a class of luminescent materials which have been proved to be excellent for applications in field emission displays and cathode ray tubes, plasma display panels. Under UV irradiation Eu+++ doped Y2O3 is a red phosphor and Tb+++ doped Y 2O3 is a green phosphor. It is possible that, due to their high quantum efficiency, they might serve as improved luminescent markers for identification of biomolecules, as already reported for CdSe and CdSe/ZnS nanocrystals. However, for any biological applications these particle powders must be suspended in water while retaining their phosphorescence. We hereby report synthesis and characterization of Eu+++ and Tb+++ doped yttrium oxide nanoparticles by sol-gel and hydrothermal processes. Eu+++ and Tb+++ doped Y2O3 nanoparticles have been synthesized by hydrothermal process using yttrium oxo isopropoxide [Y5O(OPri)13] (crystallized twice) and it’s acetyl acetone modified product [Y(O)(acac)] as precursors. Generally the sol-gel derived metal oxides are required to be annealed to the temperature ranging from 400°C-800°C in order to develop crystalline phases. However, this annealing also results in the development of aggregates which are undesirable for bio-conjugation experiments. In the hydrothermal process, we have achieved crystallinity of the nanoparticles at 300°C and the development of crystalline phases has been found to be proportional to the time of heating of the reactor. The average particle sizes as calculated from XRD were found to be 28 nm, 32 nm, and 34 nm by hydrothermal process. The particles were successfully suspended in chloroform in the presence of trioctyl phosphene oxide and TEM investigations showed the presence of single particles along with agglomerates.

Keywords: nanophosphors, Y2O3:Eu+3, Y2O3:Tb+3, sol-gel, hydrothermal method, TEM, XRD

Procedia PDF Downloads 386
1996 Removal of Nitrate and Phosphates from Waste Water Using Activated Bio-Carbon Produced from Agricultural Waste

Authors: Kgomotso Matobole, Natania De Wet, Tefo Mbambo, Hilary Rutto, Tumisang Seodigeng

Abstract:

Nitrogen and phosphorus are nutrients which are required in the ecosystem, however, at high levels, these nutrients contribute to the process of eutrophication in the receiving water bodies, which threatens aquatic organisms. Hence it is vital that they are removed before the water is discharged. This phenomenon increases the cost related to wastewater treatment. This raises the need for the development of processes that are cheaper. Activated biocarbon was used in batch and filtration system to remove nitrates and phosphates. The batch system has higher nutrients removal capabilities than the filtration system. For phosphate removal, 93 % removal is achieved at the adsorbent of 300 g while for nitrates, 84 % removal is achieved when 200 g of activated carbon is loaded.

Keywords: waste water treatment, phosphates, nitrates, activated carbon, agricultural waste

Procedia PDF Downloads 391
1995 Utilization of Low-Cost Adsorbent Fly Ash for the Removal of Phenol from Water

Authors: Ihsanullah, Muataz Ali Atieh

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In this study, a low-cost adsorbent carbon fly ash (CFA) was used for the removal of Phenol from the water. The adsorbent characteristics were observed by the Thermogravimetric Analysis (TGA), BET specific surface area analyzer, Zeta Potential and Field Emission Scanning Electron Microscopy (FE-SEM). The effect of pH, agitation speed, contact time, adsorbent dosage, and initial concentration of phenol were studied on the removal of phenol from the water. The optimum values of these variables for maximum removal of phenol were also determined. Both Freundlich and Langmuir isotherm models were successfully applied to describe the experimental data. Results showed that low-cost adsorbent phenol can be successfully applied for the removal of Phenol from the water.

Keywords: phenol, fly ash, adsorption, carbon adsorbents

Procedia PDF Downloads 304
1994 Nucleophile Mediated Addition-Fragmentation Generation of Aryl Radicals from Aryl Diazonium Salts

Authors: Elene Tatunashvili, Bun Chan, Philippe E. Nashar, Christopher S. P. McErlean

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The reduction of aryl diazonium salts is one of the most efficient ways to generate aryl radicals for use in a wide range of transformations, including Sandmeyer-type reactions, Meerwein arylations of olefins and Gomberg-Bachmann-Hey arylations of heteroaromatic systems. The aryl diazonium species can be reduced electrochemically, by UV irradiation, inner-sphere and outer-sphere single electron transfer processes (SET) from metal salts, SET from photo-excited organic catalysts or fragmentation of adducts with weak bases (acetate, hydroxide, etc.). This paper details an approach for the metal-free reduction of aryl diazonium salts, which facilitates the efficient synthesis of various aromatic compounds under exceedingly mild reaction conditions. By measuring the oxidation potential of a number of organic molecules, a series of nucleophiles were identified that reduce aryl diazonium salts via the addition-fragmentation mechanism. This approach leads to unprecedented operational simplicity: The reactions are very rapid and proceed in the open air; there is no need for external irradiation or heating, and the process is compatible with a large number of radical reactions. We illustrate these advantages by using the addition-fragmentation strategy to regioselectively arylate a series of heterocyclic compounds, to synthesize ketones by arylation of silyl enol ethers, and to synthesize benzothiophene and phenanthrene derivatives by radical annulation reactions.

Keywords: diazonium salts, hantzsch esters, oxygen, radical reactions, synthetic methods

Procedia PDF Downloads 136