Search results for: Biodegradable metal
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 2819

Search results for: Biodegradable metal

1889 Nutritional Quality Assessment and Safety Evaluation of Food Crops

Authors: Olawole Emmanuel Aina, Liziwe Lizbeth Mugivhisa, Joshua Oluwole Olowoyo, Chikwela Lawrence Obi

Abstract:

In sustained and consistent efforts to improve food security, numerous and different methods are proposed and used in the production of food crops, and farm produce to meet the demands of consumers. However, unregulated and indiscriminate methods of production present another problem that may expose consumers of these food crops to potential health risks. Therefore, it is imperative that a thorough assessment of farm produce is carried out due to the growing trend of health-conscious consumers preference for minimally processed or raw farm produce. This study evaluated the safety and nutritional quality of food crops. The objectives were to compare the nutritional quality of organic and inorganic farm produce in one hand and, on the other, evaluate the safety of farm produce with respect to trace metal and pathogenic contamination. We conducted a broad systematic search of peer-reviewed published literatures from databases and search engines such as science direct, web-of-science, Google scholar, and Scopus. This study concluded that there is no conclusive evidence to support the notion of nutritional superiority of organic food crops over their inorganic counterparts and there are documented reports of pathogenic and metal contaminations of food crops.

Keywords: food crops, fruits and vegetables, pathogens, nutrition, trace metals

Procedia PDF Downloads 80
1888 Comparative Analysis of Photosynthetic and Antioxidative Responses of Two Species of Anabaena under Ni and As(III) Stress

Authors: Shivam Yadav, Neelam Atri

Abstract:

Cyanobacteria, the photosynthetic prokaryotes are indispensable components of paddy soil contribute substantially to the nitrogen economy however often appended with metal load. They are well known to play crucial roles in maintenance of soil fertility and rice productivity. Nickel is one such metal that plays a vital role in the cellular physiology, however at higher concentrations it exerts adverse effects. Arsenic is another toxic metalloid that negatively affects the cyanobacterial proliferation. However species-specific comparative responses under As and Ni is largely unknown. The present study focuses on the comparative effects of nickel (Ni2+) and arsenite (As(III)) on two diazotrophic cyanobacterial species (Anabaena doliolum and Anabaena sp. PCC7120) in terms of antioxidative aspects. Oxidative damage measured in terms of lipid peroxidation and peroxide content was significantly higher after As(III) than Ni treatment as compared to control. Similarly, all the studied enzymatic and non-enzymatic parameters of antioxidative defense system except glutathione reductase (GR) showed greater induction against As(III) than Ni. Moreover, integrating comparative analysis of all studied parameters also demonstrated interspecies variation in terms of stress adaptive strategies reflected through higher sensitivity of Anabaena doliolum over Anabaena PCC7120.

Keywords: antioxidative system, arsenic, cyanobacteria, nickel

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1887 Development and Characterization of Cathode Materials for Sodium-Metal Chloride Batteries

Authors: C. D’Urso, L. Frusteri, M. Samperi, G. Leonardi

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Solid metal halides are used as active cathode ingredients in the case of Na-NiCl2 batteries that require a fused secondary electrolyte, sodium tetrachloraluminate (NaAlCl4), to facilitate the movement of the Na+ ion into the cathode. The sodium-nickel chloride (Na - NiCl2) battery has been extensively investigated as a promising system for large-scale energy storage applications. The growth of Ni and NaCl particles in the cathodes is one of the most important factors that degrade the performance of the Na-NiCl2 battery. The larger the particles of active ingredients contained in the cathode, the smaller the active surface available for the electrochemical reaction. Therefore, the growth of Ni and NaCl particles can lead to an increase in cell polarization resulting from the reduced active area. A higher current density, a higher state of charge (SOC) at the end of the charge (EOC) and a lower Ni / NaCl ratio are the main parameters that result in the rapid growth of Ni particles. In light of these problems, cathode and chemistry Nano-materials with recognized and well-documented electrochemical functions have been studied and manufactured to simultaneously improve battery performance and develop less expensive and more performing, sustainable and environmentally friendly materials. Starting from the well-known cathodic material (Na-NiCl2), the new electrolytic materials have been prepared on the replacement of nickel with iron (10-90%substitution of Nichel with Iron), to obtain a new material with potential advantages compared to current battery technologies; for example,, (1) lower cost of cathode material compared to state of the art as well as (2) choices of cheaper materials (stainless steels could be used for cell components, including cathode current collectors and cell housings). The study on the particle size of the cathode and the physicochemical characterization of the cathode was carried out in the test cell using, where possible, the GITT method (galvanostatic technique of intermittent titration). Furthermore, the impact of temperature on the different cathode compositions of the positive electrode was studied. Especially the optimum operating temperature is an important parameter of the active material.

Keywords: critical raw materials, energy storage, sodium metal halide, battery

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1886 3-D Strain Imaging of Nanostructures Synthesized via CVD

Authors: Sohini Manna, Jong Woo Kim, Oleg Shpyrko, Eric E. Fullerton

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CVD techniques have emerged as a promising approach in the formation of a broad range of nanostructured materials. The realization of many practical applications will require efficient and economical synthesis techniques that preferably avoid the need for templates or costly single-crystal substrates and also afford process adaptability. Towards this end, we have developed a single-step route for the reduction-type synthesis of nanostructured Ni materials using a thermal CVD method. By tuning the CVD growth parameters, we can synthesize morphologically dissimilar nanostructures including single-crystal cubes and Au nanostructures which form atop untreated amorphous SiO2||Si substrates. An understanding of the new properties that emerge in these nanostructures materials and their relationship to function will lead to for a broad range of magnetostrictive devices as well as other catalysis, fuel cell, sensor, and battery applications based on high-surface-area transition-metal nanostructures. We use coherent X-ray diffraction imaging technique to obtain 3-D image and strain maps of individual nanocrystals. Coherent x-ray diffractive imaging (CXDI) is a technique that provides the overall shape of a nanostructure and the lattice distortion based on the combination of highly brilliant coherent x-ray sources and phase retrieval algorithm. We observe a fine interplay of reduction of surface energy vs internal stress, which plays an important role in the morphology of nano-crystals. The strain distribution is influenced by the metal-substrate interface and metal-air interface, which arise due to differences in their thermal expansion. We find the lattice strain at the surface of the octahedral gold nanocrystal agrees well with the predictions of the Young-Laplace equation quantitatively, but exhibits a discrepancy near the nanocrystal-substrate interface resulting from the interface. The strain in the bottom side of the Ni nanocube, which is contacted on the substrate surface is compressive. This is caused by dissimilar thermal expansion coefficients between Ni nanocube and Si substrate. Research at UCSD support by NSF DMR Award # 1411335.

Keywords: CVD, nanostructures, strain, CXRD

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1885 Supramolecular Approach towards Novel Applications: Battery, Band Gap and Gas Separation

Authors: Sudhakara Naidu Neppalli, Tejas S. Bhosale

Abstract:

It is well known that the block copolymer (BCP) can form a complex molecule, through non-covalent bonds such as hydrogen bond, ionic bond and co-ordination bond, with low molecular weight compound as well as with macromolecules, which provide vast applications, includes the alteration of morphology and properties of polymers. Hence we covered the research that, the importance of non-covalent bonds in increasing the non-favourable segmental interactions of the blocks was well examined by attaching and detaching the bonds between the BCP and additive. We also monitored the phase transition of block copolymer and effective interaction parameter (χeff) for Li-doped polymers using small angle x-ray scattering and transmission electron microscopy. The effective interaction parameter (χeff) between two block components was evaluated using Leibler theory based on the incompressible random phase approximation (RPA) for ionized BCP in a disordered state. Furthermore, conductivity experiments demonstrate that the ionic conductivity in the samples quenched from the different structures is morphology-independent, while it increases with increasing ion salt concentration. Morphological transitions, interaction parameter, and thermal stability also examined in quarternized block copolymer. D-spacing was used to estimate effective interaction parameter (χeff) of block components in weak and strong segregation regimes of ordered phase. Metal-containing polymer has been the topic of great attention in recent years due to their wide range of potential application. Similarly, metal- ligand complex is used as a supramolecular linker between the polymers giving rise to a ‘Metallo-Supramolecule assembly. More precisely, functionalized polymer end capped with 2, 2’:6’, 2”- terpyridine ligand can be selectively complexed with wide range of transition metal ions and then subsequently attached to other terpyridine terminated polymer block. In compare to other supramolecular assembly, BCP involved metallo-supramolecule assembly offers vast applications such as optical activity, electrical conductivity, luminescence and photo refractivity.

Keywords: band gap, block copolymer, conductivity, interaction parameter, phase transition

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1884 Optimized Parameters for Simultaneous Detection of Cd²⁺, Pb²⁺ and CO²⁺ Ions in Water Using Square Wave Voltammetry on the Unmodified Glassy Carbon Electrode

Authors: K. Sruthi, Sai Snehitha Yadavalli, Swathi Gosh Acharyya

Abstract:

Water is the most crucial element for sustaining life on earth. Increasing water pollution directly or indirectly leads to harmful effects on human life. Most of the heavy metal ions are harmful in their cationic form. These heavy metal ions are released by various activities like disposing of batteries, industrial wastes, automobile emissions, and soil contamination. Ions like (Pb, Co, Cd) are carcinogenic and show many harmful effects when consumed more than certain limits proposed by WHO. The simultaneous detection of the heavy metal ions (Pb, Co, Cd), which are highly toxic, is reported in this study. There are many analytical methods for quantifying, but electrochemical techniques are given high priority because of their sensitivity and ability to detect and recognize lower concentrations. Square wave voltammetry was preferred in electrochemical methods due to the absence of background currents which is interference. Square wave voltammetry was performed on GCE for the quantitative detection of ions. Three electrode system consisting of a glassy carbon electrode as the working electrode (3 mm diameter), Ag/Agcl electrode as the reference electrode, and a platinum wire as the counter electrode was chosen for experimentation. The mechanism of detection was done by optimizing the experimental parameters, namely pH, scan rate, and temperature. Under the optimized conditions, square wave voltammetry was performed for simultaneous detection. Scan rates were varied from 5 mV/s to 100 mV/s and found that at 25 mV/s all the three ions were detected simultaneously with proper peaks at particular stripping potential. The variation of pH from 3 to 8 was done where the optimized pH was taken as pH 5 which holds good for three ions. There was a decreasing trend at starting because of hydrogen gas evolution, and after pH 5 again there was a decreasing trend that is because of hydroxide formation on the surface of the working electrode (GCE). The temperature variation from 25˚C to 45˚C was done where the optimum temperature concerning three ions was taken as 35˚C. Deposition and stripping potentials were given as +1.5 V and -1.5 V, and the resting time of 150 seconds was given. Three ions were detected at stripping potentials of Cd²⁺ at -0.84 V, Pb²⁺ at -0.54 V, and Co²⁺ at -0.44 V. The parameters of detection were optimized on a glassy carbon electrode for simultaneous detection of the ions at lower concentrations by square wave voltammetry.

Keywords: cadmium, cobalt, lead, glassy carbon electrode, square wave anodic stripping voltammetry

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1883 3D Simulation and Modeling of Magnetic-Sensitive on n-type Double-Gate Metal-Oxide-Semiconductor Field-Effect Transistor (DGMOSFET)

Authors: M. Kessi

Abstract:

We investigated the effect of the magnetic field on carrier transport phenomena in the transistor channel region of Double-Gate Metal-Oxide-Semiconductor Field-Effect Transistor (MOSFET). This explores the Lorentz force and basic physical properties of solids exposed to a constant external magnetic field. The magnetic field modulates the electrons and potential distribution in the case of silicon Tunnel FETs. This modulation shows up in the device's external electrical characteristics such as ON current (ION), subthreshold leakage current (IOF), the threshold voltage (VTH), the magneto-transconductance (gm) and the output magneto-conductance (gDS) of Tunnel FET. Moreover, the channel doping concentration and potential distribution are obtained using the numerical method by solving Poisson’s transport equation in 3D modules semiconductor magnetic sensors available in Silvaco TCAD tools. The numerical simulations of the magnetic nano-sensors are relatively new. In this work, we present the results of numerical simulations based on 3D magnetic sensors. The results show excellent accuracy comportment and good agreement compared with that obtained in the experimental study of MOSFETs technology.

Keywords: single-gate MOSFET, magnetic field, hall field, Lorentz force

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1882 Treatment and Characterization of Cadmium Metal From Textile Factory Wastewater by Electrochemical Process Using Aluminum Plate Electrode

Authors: Dessie Tibebe, Yeshifana Ayenew, Marye Mulugeta, Yezbie Kassa, Zerubabel Moges, Dereje Yenealem, Tarekegn Fentie, Agmas Amare, Hailu Sheferaw Ayele

Abstract:

Electrochemical treatment technology is a technique used for wastewater treatment due to its ability to eliminate impurities that are not easily removed by chemical processes. The objective of the study is the treatment and characterization of textile wastewater by an electrochemical process. The results obtained at various operational parameters indicated that at 20 minutes of electrochemical process at ( pH =7), initial concentration 10 mg/L, current density 37.5 mA/cm², voltage 9 v and temperature 25⁰C the highest removal efficiency was achieved. The kinetics of removal of selected metal by electrochemical treatment has been successfully described by the first-order rate equation. The results of microscopic techniques using SEM for the scarified electrode before treatment were uniform and smooth, but after the electrochemical process, the morphology was completely changed. This is due to the detection of the adsorbed aluminum hydroxide coming from adsorption of the conducting electrolyte, chemicals used in the experiments, alloying and the scrap impurities of the anode and cathode. The FTIR spectroscopic analysis broad bands at 3450 cm-¹ representing O-H functional groups, while the presence of H-O-H and Al-H groups are indicated by the bands at 2850-2750 cm-¹ and 1099 representing C-H functional groups.

Keywords: electrochemical, treatment, textile wastewater, kinetics, removal efficiency

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1881 The Effect of Supercritical Fluid on the Extraction Efficiency of Heavy Metal from Soil

Authors: Haifa El-Sadi, Maria Elektorowicz, Reed Rushing, Ammar Badawieh, Asif Chaudry

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Clay soils have particular properties that affect the assessment and remediation of contaminated sites. In clay soils, electro-kinetic transport of heavy metals has been carried out. The transport of these metals is predicated on maintaining a low pH throughout the cell, which, in turn, keeps the metals in the pore water phase where they are accessible to electro-kinetic transport. Supercritical fluid extraction and acid digestion were used for the analysis of heavy metals concentrations after the completion of electro-kinetic experimentation. Supercritical fluid (carbon dioxide) extraction is a new technique used to extract the heavy metal (lead, nickel, calcium and potassium) from clayey soil. The comparison between supercritical extraction and acid digestion of different metals was carried out. Supercritical fluid extraction, using ethylenediaminetetraacetic acid (EDTA) as a modifier, proved to be efficient and a safer technique than acid digestion technique in extracting metals from clayey soil. Mixing time of soil with EDTA before extracting heavy metals from clayey soil was investigated. The optimum and most practical shaking time for the extraction of lead, nickel, calcium and potassium was two hours.

Keywords: clay soil, heavy metals, supercritical fluid extraction, acid digestion

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1880 Generation of Catalytic Films of Zeolite Y and ZSM-5 on FeCrAlloy Metal

Authors: Rana Th. A. Al-Rubaye, Arthur A. Garforth

Abstract:

This work details the generation of thin films of structured zeolite catalysts (ZSM–5 and Y) onto the surface of a metal substrate (FeCrAlloy) using in-situ hydrothermal synthesis. In addition, the zeolite Y is post-synthetically modified by acidified ammonium ion exchange to generate US-Y. Finally the catalytic activity of the structured ZSM-5 catalyst films (Si/Al = 11, thickness 146 µm) and structured US–Y catalyst film (Si/Al = 8, thickness 23µm) were compared with the pelleted powder form of ZSM–5 and USY catalysts of similar Si/Al ratios. The structured catalyst films have been characterised using a range of techniques, including X-ray diffraction (XRD), Electron microscopy (SEM), Energy Dispersive X–ray analysis (EDX) and Thermogravimetric Analysis (TGA). The transition from oxide-on-alloy wires to hydrothermally synthesised uniformly zeolite coated surfaces was followed using SEM and XRD. In addition, the robustness of the prepared coating was confirmed by subjecting these to thermal cycling (ambient to 550°C). The cracking of n–heptane over the pellets and structured catalysts for both ZSM–5 and Y zeolite showed very similar product selectivities for similar amounts of catalyst with an apparent activation energy of around 60 kJ mol-1. This paper demonstrates that structured catalysts can be manufactured with excellent zeolite adherence and when suitably activated/modified give comparable cracking results to the pelleted powder forms. These structured catalysts will improve temperature distribution in highly exothermic and endothermic catalysed processes.

Keywords: FeCrAlloy, structured catalyst, zeolite Y, zeolite ZSM-5

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1879 Electronic/Optoelectronic Property Tuning in Two-Dimensional Transition Metal Dichalcogenides via High Pressure

Authors: Juan Xia, Jiaxu Yan, Ze Xiang Shen

Abstract:

The tuneable interlayer interactions in two-dimensional (2D) transition metal dichlcogenides (TMDs) offer an exciting platform for exploring new physics and applications by material variety, thickness, stacking sequence, electromagnetic filed, and stress/strain. Compared with the five methods mentioned above, high pressure is a clean and powerful tool to induce dramatic changes in lattice parameters and physical properties for 2D TMD materials. For instance, high pressure can strengthen the van der Waals interactions along c-axis and shorten the covalent bonds in atomic plane, leading to the typical first-order structural transition (2Hc to 2Ha for MoS2), or metallization. In particular, in the case of WTe₂, its unique symmetry endows the significant anisotropy and the corresponding unexpected properties including the giant magnetoresistance, pressure-induced superconductivity and Weyl semimetal states. Upon increasing pressure, the Raman peaks for WTe₂ at ~120 cm⁻¹, are gradually red-shifted and totally suppressed above 10 GPa, attributed to the possible structural instability of orthorhombic Td phase under high pressure and phase transition to a new monoclinic T' phase with inversion symmetry. Distinct electronic structures near Fermi level between the Td and T' phases may pave a feasible way to achieve the Weyl state tuning in one material without doping.

Keywords: 2D TMDs, electronic property, high pressure, first-principles calculations

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1878 Advanced Nanomaterials in Catalysis: Bridging the Gap Between Pollution Control and Renewable Energy

Authors: Abonyi Matthew Ndubuisi, Christopher Chiedozie Obi, Joseph Tagbo Nwabanne

Abstract:

This review focuses on the application of advanced nanomaterials in catalysis for pollution control and renewable energy solutions. This review provides a comprehensive examination of the latest developments in nanocatalysts, highlighting their role in addressing environmental challenges and facilitating sustainable energy solutions. The unique properties of nanomaterials, including high surface area, tunable electronic properties, and enhanced reactivity, make them ideal candidates for catalytic applications. This review explores various types of nanomaterials, such as metal nanoparticles, carbon-based nanostructures, and metal-organic frameworks, and their effectiveness in processes like photocatalysis, electrocatalysis, and hydrogen production. Additionally, the review discusses the environmental benefits of using nanocatalysts in pollution control, focusing on the degradation of pollutants in water and air. The potential of these materials to bridge the gap between environmental remediation and clean energy production is emphasized, showcasing their dual role in mitigating pollution and advancing renewable energy technologies. In conclusion, the review analyzes the current challenges and future directions in the field, highlighting the need for continued research to improve the design and application of nanocatalysts for a sustainable future.

Keywords: nanomaterials, catalysis, pollution control, renewable energy, sustainable technology

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1877 Synthesis, Characterization and Biological Activites of Azomethine Derivatives

Authors: Lynda Golea, Rachid Chebaki

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Schiff bases contain heterocyclic structural units with N and O donor atoms which plays an important role in coordination chemistry. Azomethine groups are a broad class of widely used compounds with applications in many fields, including analytical, inorganic chemistry and biological. Schiff's base is of promising research interest due to the widespread antibacterial resistance in medical science. In addition, the research is essential to generate Schiff base metal complexes with various applications. Schiff complexes have been used as drugs and have antibacterial, antifungal, antiviral, and anti-inflammatory properties. The various donor atoms they contain offer a special ability for metal binding. In this research on the physicochemical properties of azomethine groups, we synthesized and studied the Schiff base compounds by a condensation reaction of tryptamines and acetophenone in ethanol. The structure of the prepared compound was interpreted using 1H NMR, 13C NMR, UV-vis and FT-IR. A computational analysis at the level of DFT with functional B3LYP in conjunction with the base 6-311+G (d, p) was conducted to study its electronic and molecular structure. The biological study was performed on three bacterial strains usually causing infection, including Gram-positive and Gram-negative, for antibacterial activity. Results showed moderate biological activity and proportional activity with increasing concentration.

Keywords: azomethine, HOMO, LUMO, RMN, molecular docking

Procedia PDF Downloads 63
1876 Finite Element Method for Modal Analysis of FGM

Authors: S. J. Shahidzadeh Tabatabaei, A. M. Fattahi

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Modal analysis of a FGM plate containing the ceramic phase of Al2O3 and metal phase of stainless steel 304 was performed using ABAQUS, with the assumptions that the material has an elastic mechanical behavior and its Young modulus and density are varying in thickness direction. For this purpose, a subroutine was written in FOTRAN and linked with ABAQUS. First, a simulation was performed in accordance to other researcher’s model, and then after comparing the obtained results, the accuracy of the present study was verified. The obtained results for natural frequency and mode shapes indicate good performance of user-written subroutine as well as FEM model used in present study. After verification of obtained results, the effect of clamping condition and the material type (i.e. the parameter n) was investigated. In this respect, finite element analysis was carried out in fully clamped condition for different values of n. The results indicate that the natural frequency decreases with increase of n, since with increase of n, the amount of ceramic phase in FGM plate decreases, while the amount of metal phase increases, leading to decrease of the plate stiffness and hence, natural frequency, as the Young modulus of Al2O3 is equal to 380 GPa and the Young modulus of stainless steel 304 is equal to 207 GPa.

Keywords: FGM plates, modal analysis, natural frequency, finite element method

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1875 Eco-Nanofiltration Membranes: Nanofiltration Membrane Technology Utilization-Based Fiber Pineapple Leaves Waste as Solutions for Industrial Rubber Liquid Waste Processing and Fertilizer Crisis in Indonesia

Authors: Andi Setiawan, Annisa Ulfah Pristya

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Indonesian rubber plant area reached 2.9 million hectares with productivity reached 1.38 million. High rubber productivity is directly proportional to the amount of waste produced rubber processing industry. Rubber industry would produce a negative impact on the rubber industry in the form of environmental pollution caused by waste that has not been treated optimally. Rubber industrial wastewater containing high-nitrogen compounds (nitrate and ammonia) and phosphate compounds which cause water pollution and odor problems due to the high ammonia content. On the other hand, demand for NPK fertilizers in Indonesia continues to increase from year to year and in need of ammonia and phosphate as raw material. Based on domestic demand, it takes a year to 400,000 tons of ammonia and Indonesia imports 200,000 tons of ammonia per year valued at IDR 4.2 trillion. As well, the lack of phosphoric acid to be imported from Jordan, Morocco, South Africa, the Philippines, and India as many as 225 thousand tons per year. During this time, the process of wastewater treatment is generally done with a rubber on the tank to contain the waste and then precipitated, filtered and the rest released into the environment. However, this method is inefficient and thus require high energy costs because through many stages before producing clean water that can be discharged into the river. On the other hand, Indonesia has the potential of pineapple fruit can be harvested throughout the year in all of Indonesia. In 2010, production reached 1,406,445 tons of pineapple in Indonesia or about 9.36 percent of the total fruit production in Indonesia. Increased productivity is directly proportional to the amount of pineapple waste pineapple leaves are kept continuous and usually just dumped in the ground or disposed of with other waste at the final disposal. Through Eco-Nanofiltration Membrane-Based Fiber Pineapple leaves Waste so that environmental problems can be solved efficiently. Nanofiltration is a process that uses pressure as a driving force that can be either convection or diffusion of each molecule. Nanofiltration membranes that can split water to nano size so as to separate the waste processed residual economic value that N and P were higher as a raw material for the manufacture of NPK fertilizer to overcome the crisis in Indonesia. The raw materials were used to manufacture Eco-Nanofiltration Membrane is cellulose from pineapple fiber which processed into cellulose acetate which is biodegradable and only requires a change of the membrane every 6 months. Expected output target is Green eco-technology so with nanofiltration membranes not only treat waste rubber industry in an effective, efficient and environmentally friendly but also lowers the cost of waste treatment compared to conventional methods.

Keywords: biodegradable, cellulose diacetate, fertilizers, pineapple, rubber

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1874 Lung Function, Urinary Heavy Metals And ITS Other Influencing Factors Among Community In Klang Valley

Authors: Ammar Amsyar Abdul Haddi, Mohd Hasni Jaafar

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Heavy metals are elements naturally presented in the environment that can cause adverse effect to health. But not much literature was found on effects toward lung function, where impairment of lung function may lead to various lung diseases. The objective of the study is to explore the lung function impairment, urinary heavy metal level, and its associated factors among the community in Klang valley, Malaysia. Sampling was done in Kuala Lumpur suburb public and housing areas during community events throughout March 2019 till October 2019. respondents who gave the consent were given a questionnaire to answer and was proceeded with a lung function test. Urine samples were obtained at the end of the session and sent for Inductively coupled plasma mass spectrometry (ICP-MS) analysis for heavy metal cadmium (Cd) and lead (Pb) concentration. A total of 200 samples were analysed, and of all, 52% of respondents were male, Age ranging from 18 years old to 74 years old with a mean age of 38.44. Urinary samples show that 12% of the respondent (n=22) has Cd level above than average, and 1.5 % of the respondent (n=3) has urinary Pb at an above normal level. Bivariate analysis show that there was a positive correlation between urinary Cd and urinary Pb (r= 0.309; p<0.001). Furthermore, there was a negative correlation between urinary Cd level and full vital capacity (FVC) (r=-0.202, p=0.004), Force expiratory volume at 1 second (FEV1) (r = -0.225, p=0.001), and also with Force expiratory flow between 25-75% FVC (FEF25%-75%) (r= -0.187, p=0.008). however, urinary Pb did not show any association with FVC, FEV1, FEV1/FVC, or FEF25%-75%. Multiple linear regression analysis shows that urinary Cd remained significant and negatively affect FVC% (p=0.025) and FEV1% (p=0.004) achieved from the predicted value. On top of that, other factors such as education level (p=0.013) and duration of smoking(p=0.003) may influencing both urinary Cd and performance in lung function as well, suggesting Cd as a potential mediating factor between smoking and impairment of lung function. however, there was no interaction detected between heavy metal or other influencing factor in this study. In short, there is a negative linear relationship detected between urinary Cd and lung function, and urinary Cd is likely to affects lung function in a restrictive pattern. Since smoking is also an influencing factor for urinary Cd and lung function impairment, it is highly suggested that smokers should be screened for lung function and urinary Cd level in the future for early disease prevention.

Keywords: lung function, heavy metals, community

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1873 Separation of Copper(II) and Iron(III) by Solvent Extraction and Membrane Processes with Ionic Liquids as Carriers

Authors: Beata Pospiech

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Separation of metal ions from aqueous solutions is important as well as difficult process in hydrometallurgical technology. This process is necessary for obtaining of clean metals. Solvent extraction and membrane processes are well known as separation methods. Recently, ionic liquids (ILs) are very often applied and studied as extractants and carriers of metal ions from aqueous solutions due to their good extractability properties for various metals. This work discusses a method to separate copper(II) and iron(III) from hydrochloric acid solutions by solvent extraction and transport across polymer inclusion membranes (PIM) with the selected ionic liquids as extractants/ion carriers. Cyphos IL 101 (trihexyl(tetradecyl)phosphonium chloride), Cyphos IL 104 (trihexyl(tetradecyl)phosphonium bis(2,4,4 trimethylpentyl)phosphi-nate), trioctylmethylammonium thiosalicylate [A336][TS] and trihexyl(tetradecyl)phosphonium thiosalicylate [PR4][TS] were used for the investigations. Effect of different parameters such as hydrochloric acid concentration in aqueous phase on iron(III) and copper(II) extraction has been investigated. Cellulose triacetate membranes with the selected ionic liquids as carriers have been prepared and applied for transport of iron(IIII) and copper(II) from hydrochloric acid solutions.

Keywords: copper, iron, ionic liquids, solvent extraction

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1872 Experimental Analysis of Structure Borne Noise in an Enclosure

Authors: Waziralilah N. Fathiah, A. Aminudin, U. Alyaa Hashim, T. Vikneshvaran D. Shakirah Shukor

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This paper presents the experimental analysis conducted on a structure borne noise in a rectangular enclosure prototype made by joining of sheet aluminum metal and plywood. The study is significant as many did not realized the annoyance caused by structural borne-noise. In this study, modal analysis is carried out to seek the structure’s behaviour in order to identify the characteristics of enclosure in frequency domain ranging from 0 Hz to 200 Hz. Here, numbers of modes are identified and the characteristic of mode shape is categorized. Modal experiment is used to diagnose the structural behaviour while microphone is used to diagnose the sound. Spectral testing is performed on the enclosure. It is acoustically excited using shaker and as it vibrates, the vibrational and noise responses sensed by tri-axis accelerometer and microphone sensors are recorded respectively. Experimental works is performed on each node lies on the gridded surface of the enclosure. Both experimental measurement is carried out simultaneously. The modal experimental results of the modal modes are validated by simulation performed using MSC Nastran software. In pursuance of reducing the structure borne-noise, mitigation method is used whereby the stiffener plates are perpendicularly placed on the sheet aluminum metal. By using this method, reduction in structure borne-noise is successfully made at the end of the study.

Keywords: enclosure, modal analysis, sound analysis, structure borne-noise

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1871 Characterization of Two Hybrid Welding Techniques on SA 516 Grade 70 Weldments

Authors: M. T. Z. Butt, T. Ahmad, N. A. Siddiqui

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Commercially SA 516 Grade 70 is frequently used for the manufacturing of pressure vessels, boilers and storage tanks etc. in fabrication industry. Heat input is the major parameter during welding that may bring significant changes in the microstructure as well as the mechanical properties. Different welding technique has different heat input rate per unit surface area. Materials with large thickness are dealt with different combination of welding techniques to achieve required mechanical properties. In the present research two schemes: Scheme 1: SMAW (Shielded Metal Arc Welding) & GTAW (Gas Tungsten Arc Welding) and Scheme 2: SMAW & SAW (Submerged Arc Welding) of hybrid welding techniques have been studied. The purpose of these schemes was to study hybrid welding effect on the microstructure and mechanical properties of the weldment, heat affected zone and base metal area. It is significant to note that the thickness of base plate was 12 mm, also welding conditions and parameters were set according to ASME Section IX. It was observed that two different hybrid welding techniques performed on two different plates demonstrated that the mechanical properties of both schemes are more or less similar. It means that the heat input, welding techniques and varying welding operating conditions & temperatures did not make any detrimental effect on the mechanical properties. Hence, the hybrid welding techniques mentioned in the present study are favorable to implicate for the industry using the plate thickness around 12 mm thick.

Keywords: grade 70, GTAW, hybrid welding, SAW, SMAW

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1870 Fe3O4 Decorated ZnO Nanocomposite Particle System for Waste Water Remediation: An Absorptive-Photocatalytic Based Approach

Authors: Prateek Goyal, Archini Paruthi, Superb K. Misra

Abstract:

Contamination of water resources has been a major concern, which has drawn attention to the need to develop new material models for treatment of effluents. Existing conventional waste water treatment methods remain ineffective sometimes and uneconomical in terms of remediating contaminants like heavy metal ions (mercury, arsenic, lead, cadmium and chromium); organic matter (dyes, chlorinated solvents) and high salt concentration, which makes water unfit for consumption. We believe that nanotechnology based strategy, where we use nanoparticles as a tool to remediate a class of pollutants would prove to be effective due to its property of high surface area to volume ratio, higher selectivity, sensitivity and affinity. In recent years, scientific advancement has been made to study the application of photocatalytic (ZnO, TiO2 etc.) nanomaterials and magnetic nanomaterials in remediating contaminants (like heavy metals and organic dyes) from water/wastewater. Our study focuses on the synthesis and monitoring remediation efficiency of ZnO, Fe3O4 and Fe3O4 coated ZnO nanoparticulate system for the removal of heavy metals and dyes simultaneously. Multitude of ZnO nanostructures (spheres, rods and flowers) using multiple routes (microwave & hydrothermal approach) offers a wide range of light active photo catalytic property. The phase purity, morphology, size distribution, zeta potential, surface area and porosity in addition to the magnetic susceptibility of the particles were characterized by XRD, TEM, CPS, DLS, BET and VSM measurements respectively. Further on, the introduction of crystalline defects into ZnO nanostructures can also assist in light activation for improved dye degradation. Band gap of a material and its absorbance is a concrete indicator for photocatalytic activity of the material. Due to high surface area, high porosity and affinity towards metal ions and availability of active surface sites, iron oxide nanoparticles show promising application in adsorption of heavy metal ions. An additional advantage of having magnetic based nanocomposite is, it offers magnetic field responsive separation and recovery of the catalyst. Therefore, we believe that ZnO linked Fe3O4 nanosystem would be efficient and reusable. Improved photocatalytic efficiency in addition to adsorption for environmental remediation has been a long standing challenge, and the nano-composite system offers the best of features which the two individual metal oxides provide for nanoremediation.

Keywords: adsorption, nanocomposite, nanoremediation, photocatalysis

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1869 Changes in Inorganic Element Contents in Potamogeton Natans Exposed to Cement Factory Pollution

Authors: Yavuz Demir, Mucip Genisel, Hulya Turk, Turgay Sisman, Serkan Erdal

Abstract:

In this study, the changes in contents of inorganic elements in the aquatic plant (Potamogeton natans) as a reflection of the impact of chemical nature pollution in a cement factory region (CFR) was evaluated. For this purpose, P, S, K, Ca, Fe, Cl, Mn, Cu, Zn, Mo, Ni, Si, Al, and Cd concentrations were measured in the aquatic plant (Potamogeton natans) taken from a CFR. As a control, aquatic plant was collected at a distance of 2000 m from the outer zone of the cement factory. Inorganic element compositions were measured by energy dispersive X-ray fluorescence spectrometry (EDXRF). Three aquatic plant exhibited similar changes in contents of microelements and macroelements in their leaves. P, S, K, Cl, Ca, and Mo contents in plant grown in the CFR were reduced significantly compared to control plant, whereas their contents of Al, Mn, Fe, Ni, Cu, Zn and Cd were very high. According to these findings, it is possible that aquatic plant (Potamogeton natans) inhabiting in the vicinity of cement factory sustains the deficiency of important essential elements like P, S, K, Ca, and Mo and greatly accumulate heavy metals like Al, Mn, Fe, Ni, Cu, Zn, and Cd. In addition, results of water analysis showed that heavy metal content such as Cu, Pb, Zn, Co, and Al of water taken from CFR was remarkably high than that of outer zone of CFR. These findings with relation to changes in inorganic composition can contribute to be elucidated of effect mechanism on growth and development of aquatic plant (Potamogeton natans) of pollution resulted from cement factories.

Keywords: aquatic plant, cement factory, heavy metal pollution, inorganic element, Potamogeton natans

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1868 The Depth Penetration of Beryllium-7, ⁷BE as a Tracer in the Sembrong Catchment Area Study

Authors: J. Sharib, D. N. A. Tugi, M. T. Ishak, M. I. A. Adziz

Abstract:

The main purpose of this research paper conducted was to study the penetration of ⁷Be onto the soil surface for two different seasons in different areas of agricultural activity. The study was conducted during the dry and wet seasons from January to May 2019 in the Sembrong catchment area. The Sembrong Catchment Area is located in the district of Kluang, Johor in the South of Peninsular Malaysia and was selected based on the small size of the catchment and surrounded by various agricultural activities. A total of twenty (20) core soil samples to a depth of 10 cm each were taken using a metal corer made of metal. All these samples were brought to the Radiochemistry and Environment Group (RAS), Nuclear Malaysia, Block 23, Bangi, Malaysia, to enable the preparation, drying and analysis work to be carried out. Furthermore, all samples were oven dried at 45 – 60 ºC so that the dry weight became constant and gently disaggregated. Lastly, dried samples were milled and sieved at 2 mm before being packed into a well-type container and ready for ⁷Be analysis. The result of the analysis shows that the penetration of ⁷Be into the soil surface decreases by an exponential decay. The distribution of profiles to the interior of the soil surface or ho values ranged from 1.56 to 3.62 kg m⁻² and from 2.59 to 4.17 kg m⁻² for both dry and wet seasons. Consequently, the dry season has given a lower ho value when compared to the wet season. In conclusion, ⁷Be is a very suitable tracer to be used in determining the penetration onto the soil surface or ho values for the two different seasons.

Keywords: depth penetration, dry season, wet season, sembrong catchment, well type container

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1867 Zinc Sorption by Six Agricultural Soils Amended with Municipal Biosolids

Authors: Antoine Karam, Lotfi Khiari, Bruno Breton, Alfred Jaouich

Abstract:

Anthropogenic sources of zinc (Zn), including industrial emissions and effluents, Zn–rich fertilizer materials and pesticides containing Zn, can contribute to increasing the concentration of soluble Zn at levels toxic to plants in acid sandy soils. The application of municipal sewage sludge or biosolids (MBS) which contain metal immobilizing agents on coarse-textured soils could improve the metal sorption capacity of the low-CEC soils. The purpose of this experiment was to evaluate the sorption of Zn in surface samples (0-15 cm) of six Quebec (Canada) soils amended with MBS (pH 6.9) from Val d’Or (Quebec, Canada). Soil samples amended with increasing amounts (0 to 20%) of MBS were equilibrated with various amounts of Zn as ZnCl2 in 0.01 M CaCl2 for 48 hours at room temperature. Sorbed Zn was calculated from the difference between the initial and final Zn concentration in solution. Zn sorption data conformed to the linear form of Freundlich equation. The amount of sorbed Zn increased considerably with increasing MBS rate. Analysis of variance revealed a highly significant effect (p ≤ 0.001) of soil texture and MBS rate on the amount of sorbed Zn. The average values of the Zn-sorption capacity of MBS-amended coarse-textured soils were lower than those of MBS-amended fine textured soils. The two sandy soils (86-99% sand) amended with MBS retained 2- to 5-fold Zn than those without MBS (control). Significant Pearson correlation coefficients between the Zn sorption isotherm parameter, i.e. the Freundlich sorption isotherm (KF), and commonly measured physical and chemical entities were obtained. Among all the soil properties measured, soil pH gave the best significant correlation coefficients (p ≤ 0.001) for soils receiving 0, 5 and 10% MBS. Furthermore, KF values were positively correlated with soil clay content, exchangeable basic cations (Ca, Mg or K), CEC and clay content to CEC ratio. From these results, it can be concluded that (i) municipal biosolids provide sorption sites that have a strong affinity for Zn, (ii) both soil texture, especially clay content, and soil pH are the main factors controlling anthropogenic Zn sorption in the municipal biosolids-amended soils, and (iii) the effect of municipal biosolids on Zn sorption will be more pronounced for a sandy soil than for a clay soil.

Keywords: metal, recycling, sewage sludge, trace element

Procedia PDF Downloads 284
1866 Multi-Factor Optimization Method through Machine Learning in Building Envelope Design: Focusing on Perforated Metal Façade

Authors: Jinwooung Kim, Jae-Hwan Jung, Seong-Jun Kim, Sung-Ah Kim

Abstract:

Because the building envelope has a significant impact on the operation and maintenance stage of the building, designing the facade considering the performance can improve the performance of the building and lower the maintenance cost of the building. In general, however, optimizing two or more performance factors confronts the limits of time and computational tools. The optimization phase typically repeats infinitely until a series of processes that generate alternatives and analyze the generated alternatives achieve the desired performance. In particular, as complex geometry or precision increases, computational resources and time are prohibitive to find the required performance, so an optimization methodology is needed to deal with this. Instead of directly analyzing all the alternatives in the optimization process, applying experimental techniques (heuristic method) learned through experimentation and experience can reduce resource waste. This study proposes and verifies a method to optimize the double envelope of a building composed of a perforated panel using machine learning to the design geometry and quantitative performance. The proposed method is to achieve the required performance with fewer resources by supplementing the existing method which cannot calculate the complex shape of the perforated panel.

Keywords: building envelope, machine learning, perforated metal, multi-factor optimization, façade

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1865 High Temperature Properties of Diffusion Brazed Joints of in 939 Ni-Base Superalloy

Authors: Hyunki Kang, Hi Won Jeong

Abstract:

The gas turbine operates for a long period of time under harsh, cyclic conditions of high temperature and pressure, where high turbine inlet temperature (TIT) can range from 1273 to 1873K. Therefore, Ni-base superalloys such as IN738, IN939, Rene 45, Rene 71, Rene 80, Mar M 247, CM 247, and CMSX-4 with excellent mechanical properties and resistance to creep, corrosion and oxidation at high temperatures are indeed used. Among the alloying additions for these alloys, aluminum (Al) and titanium (Ti) form gamma prime and enhance the high-temperature properties. However, when crack-damaged high-temperature turbine components such as blade and vane are repaired by fusion welding, they cause cracks. For example, when arc welding is applied to certain superalloys that contain Al and Ti with more than 3 wt.% and T3.5 wt%, respectively, such as IN738, IN939, Rene 80, Mar M 247, and CM 247, aging cracks occur. Therefore, repair technologies using diffusion brazing, which has less heat input into the base material, are being developed. Analysis of microstructural evolution of the brazed joints with a base metal of IN 939 Ni-base superalloy using brazing different filler metals was also carried out using X-ray diffraction, OEM, SEM-EDS, and EPMA. Stress rupture and high-temperature tensile strength properties were also measured to analyze the effects of different brazing heat cycles. The boron amount in the diffusion-affected zone (DAZ) was decreased towards the base metal and the formation of borides at grain boundaries was detected through EPMA.

Keywords: gas turbine, diffusion brazing, superalloy, gas turbine repair

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1864 3D Nanostructured Assembly of 2D Transition Metal Chalcogenide/Graphene as High Performance Electrocatalysts

Authors: Sunil P. Lonkar, Vishnu V. Pillai, Saeed Alhassan

Abstract:

Design and development of highly efficient, inexpensive, and long-term stable earth-abundant electrocatalysts hold tremendous promise for hydrogen evolution reaction (HER) in water electrolysis. The 2D transition metal dichalcogenides, especially molybdenum disulfide attracted a great deal of interests due to its high electrocatalytic activity. However, due to its poor electrical conductivity and limited exposed active sites, the performance of these catalysts is limited. In this context, a facile and scalable synthesis method for fabrication nanostructured electrocatalysts composed 3D graphene porous aerogels supported with MoS₂ and WS₂ is highly desired. Here we developed a highly active and stable electrocatalyst catalyst for the HER by growing it into a 3D porous architecture on conducting graphene. The resulting nanohybrids were thoroughly investigated by means of several characterization techniques to understand structure and properties. Moreover, the HER performance of these 3D catalysts is expected to greatly improve in compared to other, well-known catalysts which mainly benefits from the improved electrical conductivity of the by graphene and porous structures of the support. This technologically scalable process can afford efficient electrocatalysts for hydrogen evolution reactions (HER) and hydrodesulfurization catalysts for sulfur-rich petroleum fuels. Owing to the lower cost and higher performance, the resulting materials holds high potential for various energy and catalysis applications. In typical hydrothermal method, sonicated GO aqueous dispersion (5 mg mL⁻¹) was mixed with ammonium tetrathiomolybdate (ATTM) and tungsten molybdate was treated in a sealed Teflon autoclave at 200 ◦C for 4h. After cooling, a black solid macroporous hydrogel was recovered washed under running de-ionized water to remove any by products and metal ions. The obtained hydrogels were then freeze-dried for 24 h and was further subjected to thermal annealing driven crystallization at 600 ◦C for 2h to ensure complete thermal reduction of RGO into graphene and formation of highly crystalline MoS₂ and WoS₂ phases. The resulting 3D nanohybrids were characterized to understand the structure and properties. The SEM-EDS clearly reveals the formation of highly porous material with a uniform distribution of MoS₂ and WS₂ phases. In conclusion, a novice strategy for fabrication of 3D nanostructured MoS₂-WS₂/graphene is presented. The characterizations revealed that the in-situ formed promoters uniformly dispersed on to few layered MoS₂¬-WS₂ nanosheets that are well-supported on graphene surface. The resulting 3D hybrids hold high promise as potential electrocatalyst and hydrodesulfurization catalyst.

Keywords: electrocatalysts, graphene, transition metal chalcogenide, 3D assembly

Procedia PDF Downloads 136
1863 The Effects of Gas Metal Arc Welding Parameters on the Corrosion Behaviour of Austenitic Stainless Steel Immersed in Aqueous Sodium Hydroxide

Authors: I. M. B. Omiogbemi, D. S. Yawas, I. M. Dagwa, F. G. Okibe

Abstract:

This work present the effects of some gas metal arc welding parameters on the corrosion behavior of austenitic stainless steel, exposed to 0.5M sodium hydroxide at ambient temperatures (298K) using conventional weight loss determination, together with surface morphology evaluation by scanning electron microscopy and the application of factorial design of experiment to determine welding conditions which enhance the integrity of the welded stainless steel. The welding variables evaluated include speed, voltage and current. Different samples of the welded stainless steels were immersed in the corrosion environment for 8, 16, 24, 32 and 40 days and weight loss determined. From the results, it was found that increase in welding current and speed at constant voltage gave the optimum performance of the austenitic stainless steel in the environment. At a of speed 40cm/min, 110Amp current and voltage of 230 volt the welded stainless steel showed only a 0.0015mg loss in weight after 40 days. Pit-like openings were observed on the surface of the metals indicating corrosion but were minimal at the optimum conditions. It was concluded from the research that relatively high welding speed and current at a constant voltage gives a good welded austenitic stainless steel with better integrity.

Keywords: welding, current, speed, austenitic stainless steel, sodium hydroxide

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1862 Municipal Sewage Sludge as Co-Substrate in Anaerobic Digestion of Vegetable Waste and Biogas Yield

Authors: J. V. Thanikal, M. Torrijos, Philipe Sousbie, S. M. Rizwan, R. Senthil Kumar, Hatem Yezdi

Abstract:

Co-digestion is one of the advantages of anaerobic digestion process because; several wastes having complimentary characteristics can be treated in a single process. The anaerobic co-digestion process, which can be defined as the simultaneous treatment of two –or more – organic biodegradable waste streams by anaerobic digestion offers great potential for the proper disposal of the organic fraction of solid waste coming from source or separate collection systems. The results of biogas production for sewage sludge, when used as a single substrate, were low (350ml/d), and also the biodegradation rate was slow. Sewage sludge as a co-substrate did not show much effect on biogas yield. The vegetable substrates (Potato, Carrot, Spinach) with a total charge of 27–36 g VS, with a HRT starting from 3 days and ending with 1 day, shown a considerable increase in biogas yield 3.5-5 l/d.

Keywords: anaerobic digestion, co-digestion, vegetable substrate, sewage sludge

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1861 Municipal Solid Waste Management in an Unplanned Hill Station in India

Authors: Moanaro Ao, Nzanthung Ngullie

Abstract:

Municipal solid waste management (MSWM) has unique challenges in hilly urban settlements. Efforts have been taken by municipalities, private players, non-governmental organizations, etc. for managing solid waste by preventing its generation, reusing, and recovering them into useful products to the extent possible, thereby minimizing its impact on the environment and human health. However, there are many constraints that lead to inadequate management of solid waste. Kohima is an unplanned hill station city in the North Eastern Region of India. The city is facing numerous issues due to the mismanagement of the MSW generated. Kohima Municipal Council (KMC) is the Urban Local Body (ULB) responsible for providing municipal services. The present MSWM system in Kohima comprises of collection, transportation, and disposal of waste without any treatment. Several efforts and experimental projects on waste management have been implemented without any success. Waste management in Kohima city is challenging due to its remote location, difficult topography, dispersed settlements within the city, sensitive ecosystem, etc. Furthermore, the narrow road network in Kohima with limited scope for expansion, inadequate infrastructure facilities, and financial constraints of the ULB add up to the problems faced in managing solid waste. This hill station also has a unique system of traditional local self-governance. Thus, shifting from a traditional system to a modern system in implementing systematic and scientific waste management is also a challenge in itself. This study aims to analyse the existing situation of waste generation, evaluate the effectiveness of the existing management system of MSW, and evolve a strategic approach to achieve a sustainable and resilient MSWM system. The results from the study show that a holistic approach, including social aspects, technical aspects, environmental aspects, and financial aspects, is needed to reform the MSWM system. Stringent adherence to source segregation is required by encouraging public participation through awareness programs. Active involvement of community-based organizations (CBOs) has brought a positive change in sensitizing the public. A waste management model was designed to be adopted at a micro-level such as composting household biodegradable waste and incinerator plants at the community level for non-biodegradable waste. Suitable locations for small waste stations were identified using geographical information system (GIS) tools for waste recovery and recycling. Inculcating the sense of responsibility in every waste generator towards waste management by implementing incentive-based strategies at the Ward level was explored. Initiatives based on the ‘polluters pay principle’ were also explored to make the solid waste management model “self-sustaining”.

Keywords: municipal solid waste management, public participation, source segregation, sustainable

Procedia PDF Downloads 68
1860 Transition Metal Bis(Dicarbollide) Complexes in Design of Molecular Switches

Authors: Igor B. Sivaev

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

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

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