Search results for: pseudo‐enantiomers
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 457

Search results for: pseudo‐enantiomers

157 State Estimator Performance Enhancement: Methods for Identifying Errors in Modelling and Telemetry

Authors: M. Ananthakrishnan, Sunil K Patil, Koti Naveen, Inuganti Hemanth Kumar

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State estimation output of EMS forms the base case for all other advanced applications used in real time by a power system operator. Ensuring tuning of state estimator is a repeated process and cannot be left once a good solution is obtained. This paper attempts to demonstrate methods to improve state estimator solution by identifying incorrect modelling and telemetry inputs to the application. In this work, identification of database topology modelling error by plotting static network using node-to-node connection details is demonstrated with examples. Analytical methods to identify wrong transmission parameters, incorrect limits and mistakes in pseudo load and generator modelling are explained with various cases observed. Further, methods used for active and reactive power tuning using bus summation display, reactive power absorption summary, and transformer tap correction are also described. In a large power system, verifying all network static data and modelling parameter on regular basis is difficult .The proposed tuning methods can be easily used by operators to quickly identify errors to obtain the best possible state estimation performance. This, in turn, can lead to improved decision-support capabilities, ultimately enhancing the safety and reliability of the power grid.

Keywords: active power tuning, database modelling, reactive power, state estimator

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156 Development of Mineral Carbonation Process from Ultramafic Tailings, Enhancing the Reactivity of Feedstocks

Authors: Sara Gardideh, Mansoor Barati

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The mineral carbonation approach for reducing global warming has garnered interest on a worldwide scale. Due to the benefits of permanent storage and abundant mineral resources, mineral carbonation (MC) is one of the most effective strategies for sequestering CO₂. The combination of mineral processing for primary metal recovery and mineral carbonation for carbon sequestration is an emerging field of study with the potential to minimize capital costs. A detailed study of low-pressures–solid carbonation of ultramafic tailings in a dry environment has been accomplished. In order to track the changing structure of serpentine minerals and their reactivity as a function of temperature (300-900 ᵒC), CO₂ partial pressure (25-90 mol %), and thermal preconditioning, thermogravimetry has been utilized. The incongruent CO₂ van der Waals molecular diameters with the octahedral-tetrahedral lattice constants of serpentine were used to explain the mild carbonation reactivity. Serpentine requires additional thermal-treatment to remove hydroxyl groups, resulting in the chemical transformation to pseudo-forsterite, which is a mineral composed of isolated SiO₄ tetrahedra linked by octahedrally coordinated magnesium ions. The heating treatment above 850 ᵒC is adequate to remove chemically bound water from the lattice. Particles with a diameter < 34 (μm) are desirable, and thermally treated serpentine at 850 ᵒC for 2.30 hours reached 65% CO₂ storage capacity. The decrease in particle size, increase in temperature, and magnetic separation can dramatically enhance carbonation.

Keywords: particle size, thermogravimetry, thermal-treatment, serpentine

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155 Toxic Dyes Removal in Aqueous Solution Using Calcined and Uncalcined Anionic Clay Zn/Al+Fe

Authors: Bessaha Hassiba, Bouraada Mohamed

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Layered double hydroxide with Zn/(Al+Fe) molar ratio of 3:1 was synthesized by co-precipitation method and their calcined product was obtained by heating treatment of ZAF-HT at 500°C. The calcined and uncalcined materials were used to remove weak acid dyes: indigo carmine (IC) and green bezanyl-F2B (F2B) in aqueous solution. The synthesized materials were characterized by XRD, SEM, FTIR and TG/DTA analysis confirming the formation of pure layered structure of ZAF-HT, the destruction of the original structure after calcination and the intercalation of the dyes molecules. Moreover, the interlayer distance increases from 7.645 Å in ZAF-HT to 19.102 Å after the dyes sorption. The dose of the adsorbents was chosen 0.5 g/l while the initial concentrations were 250 and 750 mg/l for indigo carmine and green bezanyl-F2B respectively. The sorption experiments were carried out at ambient temperature and without adjusting the initial solution pH (pHi = 6.10 for IC and pHi = 5.01 for F2B). In addition, the maximum adsorption capacities obtained by ZAF-HT and CZAF for both dyes followed the order: CZAF-F2B (1501.4 mg.g-1) > CZAF-IC (617.3 mg.g-1) > ZAF-HT-IC (41.4 mg.g-1) > ZAF-HT-F2B (28.9 mg.g-1). The removal of indigo carmine and green bezanyl-F2B by ZAF-HT was due to the anion exchange and/or the adsorption on the surface. By using the calcined material (CZAF), the removal of the dyes was based on a particular property, called ‘memory effect’. CZAF recover the pristine structure in the presence anionic molecules such as acid dyes where they occupy the interlayer space. The sorption process was spontaneous in nature and followed pseudo-second-order. The isotherms showed that the removal of IC and F2B by ZAF-HT and CZAF were consistent with Langmiur model.

Keywords: acid dyes, adsorption, calcination, layered double hydroxides

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154 Fabrication of Electrospun Carbon Nanofibers-Reinforced Chitosan-Based Hydrogel for Environmental Applications

Authors: Badr M. Thamer

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The use of hydrogels as adsorbents for pollutants removal from wastewater is limited due to their high swelling properties and the difficulty in recovering them after the adsorption process. To overcome these problems, a new hydrogel nanocomposite based on chitosan-g-polyacrylic acid/oxidized electrospun carbon nanofibers (CT-g-PAA/O-ECNFs) was prepared by in-situ grafting polymerization process. The prepared hydrogel nanocomposite was used as a novel effective and highly reusable adsorbent for the removal of methylene blue (MB) from polluted water with low cost. The morphology and the structure of CT-g-PAA/O-ECNFs were investigated by numerous techniques. The effect of incorporating O-ECNFs on the swelling capability of the prepared hydrogel was explored in distillated water and MB solution at normal pH. The effect of parameters including the ratio of O-ECNFs, contact time, pH, initial concentration, and temperature on the adsorption process were explored. The adsorption isotherm and kinetic were studied by numerous non-linear models. The obtained results confirmed that the incorporation of O-ECNFs into the hydrogel network improved its ability towards MB dye removal with decreasing their swelling capacity. The adsorption process depends on the pH value of the dye solution. Additionally, the adsorption and kinetic results were fitted using the Freundlich isotherm model and pseudo second order model (PSO), respectively. Moreover, the new adsorbents can be recycled for at least five cycles keeping its adsorption capacity and can be easily recovered without loss in its initial weight.

Keywords: carbon nanofibers, hydrogels, nanocomposites, water treatment

Procedia PDF Downloads 147
153 The Relationship between Coping Styles and Internet Addiction among High School Students

Authors: Adil Kaval, Digdem Muge Siyez

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With the negative effects of internet use in a person's life, the use of the Internet has become an issue. This subject was mostly considered as internet addiction, and it was investigated. In literature, it is noteworthy that some theoretical models have been proposed to explain the reasons for internet addiction. In addition to these theoretical models, it may be thought that the coping style for stressing events can be a predictor of internet addiction. It was aimed to test with logistic regression the effect of high school students' coping styles on internet addiction levels. Sample of the study consisted of 770 Turkish adolescents (471 girls, 299 boys) selected from high schools in the 2017-2018 academic year in İzmir province. Internet Addiction Test, Coping Scale for Child and Adolescents and a demographic information form were used in this study. The results of the logistic regression analysis indicated that the model of coping styles predicted internet addiction provides a statistically significant prediction of internet addiction. Gender does not predict whether or not to be addicted to the internet. The active coping style is not effective on internet addiction levels, while the avoiding and negative coping style are effective on internet addiction levels. With this model, % 79.1 of internet addiction in high school is estimated. The Negelkerke pseudo R2 indicated that the model accounted for %35 of the total variance. The results of this study on Turkish adolescents are similar to the results of other studies in the literature. It can be argued that avoiding and negative coping styles are important risk factors in the development of internet addiction.

Keywords: adolescents, coping, internet addiction, regression analysis

Procedia PDF Downloads 173
152 Potassium Acetate - Coconut Shell Activated Carbon for Adsorption of Benzene and Toluene: Equilibrium and Kinetic Studies

Authors: Jibril Mohammed, Usman Dadum Hamza, Abdulsalam Surajudeen, Baba Yahya Danjuma

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Considerable concerns have been raised over the presence of volatile organic compounds (VOCs) in water. In this study, coconut shell based activated carbon was produced through chemical activation with potassium acetate (PAAC) for adsorption of benzene and toluene. The porous carbons were characterized using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), proximate analysis, and ultimate analysis and nitrogen adsorption tests. Adsorption of benzene and toluene on the porous carbons were conducted at varying concentrations (50-250 mg/l). The high BET surface area of 622 m2/g and highly heteroporous adsorbent prepared gave good removal efficiencies of 79 and 82% for benzene and toluene respectively, with 32% yield. Equilibrium data were fitted to Langmuir, Freundlich and Temkin isotherms with all the models having R2 > 0.94. The equilibrium data were best represented by the Langmuir isotherm, with maximum adsorption capacity of 192 mg/g and 227 mg/g for benzene and toluene respectively. The Webber and Chakkravorti equilibrium parameter (RL) values are between 0 and 1 confirming the favourability of the Langmuir model. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The PAAC produced can be used effectively to salvage environmental pollution problems posed by VOCs through a sustainable process.

Keywords: adsorption, equilibrium and kinetics studies, potassium acetate, water treatment

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151 Efficient Mercury Sorbent: Activated Carbon and Metal Organic Framework Hybrid

Authors: Yongseok Hong, Kurt Louis Solis

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In the present study, a hybrid sorbent using the metal organic framework (MOF), UiO-66, and powdered activated carbon (pAC) is synthesized to remove cationic and anionic metals simultaneously. UiO-66 is an octahedron-shaped MOF with a Zr₆O₄(OH)₄ metal node and 1,4-benzene dicarboxylic acid (BDC) organic linker. Zr-based MOFs are attractive for trace element remediation in wastewaters, because Zr is relatively non-toxic as compared to other classes of MOF and, therefore, it will not cause secondary pollution. Most remediation studies with UiO-66 target anions such as fluoride, but trace element oxyanions such as arsenic, selenium, and antimony have also been investigated. There have also been studies involving mercury removal by UiO-66 derivatives, however these require post-synthetic modifications or have lower effective surface areas. Activated carbon is known for being a readily available, well-studied, effective adsorbent for metal contaminants. Solvothermal method was employed to prepare hybrid sorbent from UiO66 and activated carbon, which could be used to remove mercury and selenium simultaneously. The hybrid sorbent was characterized using FSEM-EDS, FT-IR, XRD, and TGA. The results showed that UiO66 and activated carbon are successfully composited. From BET studies, the hybrid sorbent has a SBET of 1051 m² g⁻¹. Adsorption studies were performed, where the hybrid showed maximum adsorption of 204.63 mg g⁻¹ and 168 mg g⁻¹ for Hg (II) and selenite, respectively, and follows the Langmuir model for both species. Kinetics studies have revealed that the Hg uptake of the hybrid is pseudo-2nd order and has rate constant of 5.6E-05 g mg⁻¹ min⁻¹ and the selenite uptake follows the simplified Elovich model with α = 2.99 mg g⁻¹ min⁻¹, β = 0.032 g mg⁻¹.

Keywords: adsorption, flue gas wastewater, mercury, selenite, metal organic framework

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150 Sulfamethoxazole Degradation by Conventional Fenton and Microwave-Assisted Fenton Reaction

Authors: Derradji Chebli, Abdallah Bouguettoucha, Zoubir Manaa, Amrane Abdeltif

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Pharmaceutical products, such as sulfamethoxazole (SMX) are rejected in the environment at trace level by human and animals (ng/L to mg/L), in their original form or as byproducts. Antibiotics are toxic contaminants for the aquatic environment, owing to their adverse effects on the aquatic life and humans. Even at low concentrations, they can negatively impact biological water treatment leading to the proliferation of antibiotics-resistant pathogens. It is therefore of major importance to develop efficient methods to limit their presence in the aquatic environment. In this aim, advanced oxidation processes (AOP) appear relevant compared to other methods, since they are based on the production of highly reactive free radicals, and especially ●OH. The objective of this work was to evaluate the degradation of SMX by microwave-assisted Fenton reaction (MW/Fe/H2O2). Hydrogen peroxide and ferrous ions concentrations, as well as the microwave power were optimized. The results showed that the SMX degradation by MW/Fe/H2O2 followed a pseudo-first order kinetic. The treatment of 20 mg/L initial SMX by the Fenton reaction in the presence of microwave showed the positive impact of this latter owing to the higher degradation yields observed in a reduced reaction time if compared to the conventional Fenton reaction, less than 5 min for a total degradation. In addition, increasing microwave power increased the degradation kinetics. Irrespective of the application of microwave, the optimal pH for the Fenton reaction remained 3. Examination of the impact of the ionic strength showed that carbonate and sulfate anions increased the rate of SMX degradation.

Keywords: antibiotic, degradation, elimination, fenton, microwave, polluant

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149 Radical Degradation of Acetaminophen with Peroxymonosulfate-Based Oxidation Processes

Authors: Chaoqun Tan, Naiyun Gao, Xiaoyan Xin

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Perxymonosulfate (PMS)-based oxidation processes, as an alternative of hydrogen peroxide-based oxidation processes, are more and more popular because of reactive radical species (SO4-•, OH•) produced in systems. Magnetic nano-scaled particles Fe3O4 and ferrous anion (Fe2+) were studied for the activation of PMS for degradation of acetaminophen (APAP) in water. The Fe3O4 MNPs were found to effectively catalyze PMS for APAP and the reactions well followed a pseudo-first-order kinetics pattern (R2>0.95). While the degradation of APAP in PMS-Fe2+ system proceeds through two stages: a fast stage and a much slower stage. Within 5 min, approximately 7% and 18% of 10 ppm APAP was accomplished by 0.2 mM PMS in Fe3O4 (0.8g/L) and Fe2+ (0.1mM) activation process. However, as reaction proceed to 120 min, approximately 75% and 35% of APAP was removed in Fe3O4 activation process and Fe2+ activation process, respectively. Within 120 min, the mineralization of APAP was about 7.5% and 5.0% (initial APAP of 10 ppm and [PMS]0 of 0.2 mM) in Fe3O4-PMS and Fe2+-PMS system, while the mineralization could be greatly increased to about 31% and 40% as [PMS]0 increased to 2.0 mM in in Fe3O4-PMS and Fe2+-PMS system, respectively. At last, the production of reactive radical species were validated directly from Electron Paramagnetic Resonance (ESR) tests with 0.1 M 5,5-Dimethyl-1-pyrrolidine N-oxide (DMPO). Plausible mechanisms on the radical generation from Fe3O4 and Fe2+ activation of PMS are proposed on the results of radial identification tests. The results demonstrated that Fe3O4 MNPs activated PMS and Fe2+ anion activated PMS systems are promising technologies for water pollution caused by contaminants such as pharmaceutical. Fe3O4-PMS system is more suitable for slowly remediation, while Fe2+-PMS system is more suitable for fast remediation.

Keywords: acetaminophen, peroxymonosulfate, radicals, Electron Paramagnetic Resonance (ESR)

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148 Structural Performance Evaluation of Concrete Beams Reinforced with Recycled and Virgin Plastic Fibres

Authors: Vighnesh Daas, David B. Tann, Mahmood Datoo

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The incorporation of recycled plastic fibres in concrete as reinforcement is a potential sustainable alternative for replacement of ordinary steel bars. It provides a scope for waste reduction and re-use of plastics in the construction industry on a large scale. Structural use of fibre reinforced concrete is limited to short span members and low reliability classes. In this study, recycled carpet fibres made of 95% polypropylene with length of 45mm were used for experimental investigations. The performance of recycled polypropylene fibres under structural loading has been compared with commercially available virgin fibres at low volume fractions of less than 1%. A series of 100 mm cubes and 125x200x2000 mm beams were used to conduct strength tests in bending and compression to measure the influence of type and volume of fibres on the structural behaviour of fibre reinforced concrete beams. The workability of the concrete mix decreased as a function of fibre content and resulted in a modification of the mix design. The beams failed in a pseudo-ductile manner with an enhanced bending capacity. The specimens showed significant improvement in the post-cracking behaviour and load carrying ability as compared to conventional reinforced concrete members. This was associated to the binding properties of the fibres in the concrete matrix. With the inclusion of fibres at low volumes of 0-0.5%, there was reduction in crack sizes and deflection. This study indicates that the inclusion of recycled polypropylene fibres at low volumes augments the structural behaviour of concrete as compared to conventional reinforced concrete as well as virgin fibre reinforced concrete.

Keywords: fibre reinforced concrete, polypropylene, recycled, strength

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147 Effect of Acid-Basic Treatments of Lingocellulosic Material Forest Wastes Wild Carob on Ethyl Violet Dye Adsorption

Authors: Abdallah Bouguettoucha, Derradji Chebli, Tariq Yahyaoui, Hichem Attout

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The effect of acid -basic treatment of lingocellulosic material (forest wastes wild carob) on Ethyl violet adsorption was investigated. It was found that surface chemistry plays an important role in Ethyl violet (EV) adsorption. HCl treatment produces more active acidic surface groups such as carboxylic and lactone, resulting in an increase in the adsorption of EV dye. The adsorption efficiency was higher for treated of lingocellulosic material with HCl than for treated with KOH. Maximum biosorption capacity was 170 and 130 mg/g, for treated of lingocellulosic material with HCl than for treated with KOH at pH 6 respectively. It was also found that the time to reach equilibrium takes less than 25 min for both treated materials. The adsorption of basic dye (i.e., ethyl violet or basic violet 4) was carried out by varying some process parameters, such as initial concentration, pH and temperature. The adsorption process can be well described by means of a pseudo-second-order reaction model showing that boundary layer resistance was not the rate-limiting step, as confirmed by intraparticle diffusion since the linear plot of Qt versus t^0.5 did not pass through the origin. In addition, experimental data were accurately expressed by the Sips equation if compared with the Langmuir and Freundlich isotherms. The values of ΔG° and ΔH° confirmed that the adsorption of EV on acid-basic treated forest wast wild carob was spontaneous and endothermic in nature. The positive values of ΔS° suggested an irregular increase of the randomness at the treated lingocellulosic material -solution interface during the adsorption process.

Keywords: adsorption, isotherm models, thermodynamic parameters, wild carob

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146 Nitrogen/Platinum Co-Doped TiO₂ for Enhanced Visible Light Photocatalytic Degradation of Brilliant Black

Authors: Sarre Nzaba, Bulelwa Ntsendwana, Bekkie Mamba, Alex Kuvarega

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Elimination of toxic organic compounds from wastewater is currently one of the most important subjects in water pollution control. The discharge of azo dyes such as Brilliant black (BB) into the water bodies has carcinogenic and mutagenic effects on humankind and the ecosystem. Conventional water treatment techniques fail to degrade these dyes completely thereby posing more problems. Advanced oxidation processes (AOPs) are promising technologies in solving the problem. Anatase type nitrogen-platinum (N,Pt) co-doped TiO₂ photocatalyts were prepared by a modified sol-gel method using amine terminated polyamidoamine generation 1 (PG1) as a template and source of nitrogen. SEM/ EDX, TEM, XRD, XPS, TGA, FTIR, RS, PL and UV-Vis were used to characterize the prepared nanomaterials. The synthesized photocatalysts exhibited lower band gap energies as compared to the commercial TiO₂ revealing a shift in band gap towards the visible light absorption region. Photocatalytic activity of N,Pt co-doped TiO₂ was measured by the reaction of photocatalytic degradation of BB dye. Enhanced photodegradation efficiency of BB was achieved after 180 min reaction time with initial concentration of 50 ppm BB solution. This was attributed to the rod-like shape of the materials, larger surface area, and enhanced absorption of visible light induced by N,Pt co-doping. The co-doped N,Pt also exhibited pseudo-first order kinetic behaviour with half-life and rate constant of 0.37 min 0.1984 min⁻¹ and respectively. N doped TiO₂ and N,Pt co-doped TiO₂ exhibited enhanced photocatalytic performances for the removal of BB from water.

Keywords: N, Pt co-doped TiO₂, dendrimer, photodegradation, visible-light

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145 Hysteresis Modeling in Iron-Dominated Magnets Based on a Deep Neural Network Approach

Authors: Maria Amodeo, Pasquale Arpaia, Marco Buzio, Vincenzo Di Capua, Francesco Donnarumma

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Different deep neural network architectures have been compared and tested to predict magnetic hysteresis in the context of pulsed electromagnets for experimental physics applications. Modelling quasi-static or dynamic major and especially minor hysteresis loops is one of the most challenging topics for computational magnetism. Recent attempts at mathematical prediction in this context using Preisach models could not attain better than percent-level accuracy. Hence, this work explores neural network approaches and shows that the architecture that best fits the measured magnetic field behaviour, including the effects of hysteresis and eddy currents, is the nonlinear autoregressive exogenous neural network (NARX) model. This architecture aims to achieve a relative RMSE of the order of a few 100 ppm for complex magnetic field cycling, including arbitrary sequences of pseudo-random high field and low field cycles. The NARX-based architecture is compared with the state-of-the-art, showing better performance than the classical operator-based and differential models, and is tested on a reference quadrupole magnetic lens used for CERN particle beams, chosen as a case study. The training and test datasets are a representative example of real-world magnet operation; this makes the good result obtained very promising for future applications in this context.

Keywords: deep neural network, magnetic modelling, measurement and empirical software engineering, NARX

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144 Modeling of Strong Motion Generation Areas of the 2011 Tohoku, Japan Earthquake Using Modified Semi-Empirical Technique Incorporating Frequency Dependent Radiation Pattern Model

Authors: Sandeep, A. Joshi, Kamal, Piu Dhibar, Parveen Kumar

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In the present work strong ground motion has been simulated using a modified semi-empirical technique (MSET), with frequency dependent radiation pattern model. Joshi et al. (2014) have modified the semi-empirical technique to incorporate the modeling of strong motion generation areas (SMGAs). A frequency dependent radiation pattern model is applied to simulate high frequency ground motion more precisely. Identified SMGAs (Kurahashi and Irikura 2012) of the 2011 Tohoku earthquake (Mw 9.0) were modeled using this modified technique. Records are simulated for both frequency dependent and constant radiation pattern function. Simulated records for both cases are compared with observed records in terms of peak ground acceleration and pseudo acceleration response spectra at different stations. Comparison of simulated and observed records in terms of root mean square error suggests that the method is capable of simulating record which matches in a wide frequency range for this earthquake and bears realistic appearance in terms of shape and strong motion parameters. The results confirm the efficacy and suitability of rupture model defined by five SMGAs for the developed modified technique.

Keywords: strong ground motion, semi-empirical, strong motion generation area, frequency dependent radiation pattern, 2011 Tohoku Earthquake

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143 Elimination of Contaminants of Emerging Concerns by Peracetic Acid and Advanced Oxidation Process

Authors: Abdul Rahim Al Umairi, Mohamed Gamal El-Din

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The removal of the selected contaminants of emerging concerns (CECs) presented under related environmental conditions by Peracetic Acid (PAA) and PAA-UV photolysis processes was examined in this study. A mixture of (CECs) (pesticides and pharmaceutical compounds) was prepared inclean water and treated with different doses of PAA (3.2, 6.4, and 9.6 mg/L) under different pH values (5.2, 7.2, and 9.2). The results revealed that the reactivity of the selected CECs with PAA was classified into three groups: Group 1 poorly reactive (removal <25%), Group2 moderately reactive (removal 25% to 50%), and Group 3 highly reactive (> 50%). Group1 includes atrazine (ATZ) and fluconazole (FCL), Group2 includes carbamazepine (CBZ), sulfamethoxazole (SMX), trimethoprim (TMP), mecoprop (MCPP), diazinon (DZN) and Group 3 includes perfluorooctanoic acid (PFOA) and clindamycin (CLN). The pH was found to affect the CECs' degradation differently, for Group 1 and Group 3, better removal was achieved in the acidand alkaline medium. In contrast, for Group 2 pH effects were not well pronounced. PAA-UV photolysis processes were explored to degrade the recalcitrant indicators compounds: ATZ (Group1) and SMX(Group2). PAA-UV process showed no improvement in the removal of ATZ. In contrast, PAA-UV removed SMX drastically with a pseudo decay rate constant of 0.014 cm2/mJ compared to 0.002 cm2/mJ by UV alone. The contribution of hydroxyl radical to the degradation process using the PAA-UV process was found to be negligible. This study illustratedPAA's capability on the degradation of the CECs presented in relative environmental conditions and unveiled the potential of using PAA-UV processes as advanced oxidation processes.

Keywords: advanced oxidation process, contaminants of emerging concerns, peracetic acid, hydroxyl radical

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142 Disassociating Preferences from Evaluations Towards Pseudo Drink Brands

Authors: Micah Amd

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Preferences towards unfamiliar drink brands can be predictably influenced following correlations of subliminally-presented brands (CS) with positively valenced attributes (US). Alternatively, evaluations towards subliminally-presented CS may be more variable, suggesting that CS-evoked evaluations may disassociate from CS-associated preferences following subliminal CS-US conditioning. We assessed this hypothesis over three experiments (Ex1, Ex2, Ex3). Across each experiment, participants first provided preferences and evaluations towards meaningless trigrams (CS) as a baseline, followed by conditioning and a final round of preference and evaluation measurements. During conditioning, four pairs of subliminal and supraliminal/visible CS were respectively correlated with four US categories varying along aggregate valence (e.g., 100% positive, 80% positive, 40% positive, 0% positive – for Ex1 and Ex2). Across Ex1 and Ex2, presentation durations for subliminal CS were 34 and 17 milliseconds, respectively. Across Ex3, aggregate valences of the four US categories were altered (75% positive, 55% positive, 45% positive, 25% positive). Valence across US categories was manipulated to address a supplemental query of whether US-to-CS valence transfer was summative or integrative. During analysis, we computed two sets of difference scores reflecting pre-post preference and evaluation performances, respectively. These were subjected to Bayes tests. Across all experiments, results illustrated US-to-CS valence transfer was most likely to shift evaluations for visible CS, but least likely to shift evaluations for subliminal CS. Alternatively, preferences were likely to shift following correlations with single-valence categories (e.g., 100% positive, 100% negative) across both visible and subliminal CS. Our results suggest that CS preferences can be influenced through subliminal conditioning even as CS evaluations remain unchanged, supporting our central hypothesis. As for whether transfer effects are summative/integrative, our results were more mixed; a comparison of relative likelihoods revealed that preferences are more likely to reflect summative effects whereas evaluations reflect integration, independent of visibility condition.

Keywords: subliminal conditioning, evaluations, preferences, valence transfer

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141 An Improved Robust Algorithm Based on Cubature Kalman Filter for Single-Frequency Global Navigation Satellite System/Inertial Navigation Tightly Coupled System

Authors: Hao Wang, Shuguo Pan

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The Global Navigation Satellite System (GNSS) signal received by the dynamic vehicle in the harsh environment will be frequently interfered with and blocked, which generates gross error affecting the positioning accuracy of the GNSS/Inertial Navigation System (INS) integrated navigation. Therefore, this paper put forward an improved robust Cubature Kalman filter (CKF) algorithm for single-frequency GNSS/INS tightly coupled system ambiguity resolution. Firstly, the dynamic model and measurement model of a single-frequency GNSS/INS tightly coupled system was established, and the method for GNSS integer ambiguity resolution with INS aided is studied. Then, we analyzed the influence of pseudo-range observation with gross error on GNSS/INS integrated positioning accuracy. To reduce the influence of outliers, this paper improved the CKF algorithm and realized an intelligent selection of robust strategies by judging the ill-conditioned matrix. Finally, a field navigation test was performed to demonstrate the effectiveness of the proposed algorithm based on the double-differenced solution mode. The experiment has proved the improved robust algorithm can greatly weaken the influence of separate, continuous, and hybrid observation anomalies for enhancing the reliability and accuracy of GNSS/INS tightly coupled navigation solutions.

Keywords: GNSS/INS integrated navigation, ambiguity resolution, Cubature Kalman filter, Robust algorithm

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140 Data Augmentation for Early-Stage Lung Nodules Using Deep Image Prior and Pix2pix

Authors: Qasim Munye, Juned Islam, Haseeb Qureshi, Syed Jung

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Lung nodules are commonly identified in computed tomography (CT) scans by experienced radiologists at a relatively late stage. Early diagnosis can greatly increase survival. We propose using a pix2pix conditional generative adversarial network to generate realistic images simulating early-stage lung nodule growth. We have applied deep images prior to 2341 slices from 895 computed tomography (CT) scans from the Lung Image Database Consortium (LIDC) dataset to generate pseudo-healthy medical images. From these images, 819 were chosen to train a pix2pix network. We observed that for most of the images, the pix2pix network was able to generate images where the nodule increased in size and intensity across epochs. To evaluate the images, 400 generated images were chosen at random and shown to a medical student beside their corresponding original image. Of these 400 generated images, 384 were defined as satisfactory - meaning they resembled a nodule and were visually similar to the corresponding image. We believe that this generated dataset could be used as training data for neural networks to detect lung nodules at an early stage or to improve the accuracy of such networks. This is particularly significant as datasets containing the growth of early-stage nodules are scarce. This project shows that the combination of deep image prior and generative models could potentially open the door to creating larger datasets than currently possible and has the potential to increase the accuracy of medical classification tasks.

Keywords: medical technology, artificial intelligence, radiology, lung cancer

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139 Surfactant-Modified Chitosan Beads: An Efficient and Cost Effective Material for Adsorptive Removal of Lead from Aqueous Solutions

Authors: Preeti Pal, Anjali Pal

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Chitosan is an effective sorbent for removal of contaminants from wastewater. However, the ability of pure chitosan is specific because of its cationic charge. It causes repulsion in the removal process of various cationic charged molecules. The present study has been carried out for the successful removal of Pb²⁺ ions from aqueous solution by modified chitosan beads. Surface modification of chitosan (CS) beads was performed by using the anionic surfactant (AS), sodium dodecyl sulfate (SDS). Micelle aggregation property of SDS has been utilized for the formation of bilayer over the CS beads to produce surfactant modified chitosan (SMCS) beads. Prepared adsorbents were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) in order to find out their composition and surface morphology. SMCS beads, when compared to the pure CS beads, showed three times higher adsorption. This higher adsorption is believed to be due to the adsolubilization of Pb²⁺ ions on SDS bilayer. This bilayer provides more adsorption sites for quick and effective removal of Pb²⁺ ions from the aqueous phase. Moreover, the kinetic and adsorption isotherm models were employed to the obtained data for the description of the lead adsorption processes. It was found that the removal kinetics follows pseudo-second order model. Adsorption isotherm data fits well to the Langmuir model. The maximum adsorption capacity obtained is 100 mg/g at the dosage of 0.675 g/L for 50 mg/L of Pb²⁺. The adsorption capacity is subject to increase with increasing the Pb²⁺ ions concentration in the solution. The results indicated that the prepared hydrogel beads are efficient adsorbent for removal of Pb²⁺ ions from the aqueous medium.

Keywords: adsolubilisation, anionic surfactant, bilayer, chitosan, Pb²⁺

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138 Impact of Social Transfers on Energy Poverty in Turkey

Authors: Julide Yildirim, Nadir Ocal

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Even though there are many studies investigating the extent and determinants of poverty, there is paucity of research investigating the issue of energy poverty in Turkey. The aim of this paper is threefold: First to investigate the extend of energy poverty in Turkey by using Household Budget Survey datasets belonging to 2005 - 2016 period. Second, to examine the risk factors for energy poverty. Finally, to assess the impact of social assistance program participation on energy poverty. Existing literature employs alternative methods to measure energy poverty. In this study energy poverty is measured by employing expenditure approach, where people are considered as energy poor if they disburse more than 10 per cent of their income to meet their energy requirements. Empirical results indicate that energy poverty rate is around 20 per cent during the time period under consideration. Since Household Budget Survey panel data is not available for 2005 - 2016 period, a pseudo panel has been constructed. Panel logistic regression method is utilized to determine the risk factors for energy poverty. The empirical results demonstrate that there is a statistically significant impact of work status and education level on energy poverty likelihood. In the final part of the paper the impact of social transfers on energy poverty has been examined by utilizing panel biprobit model, where social transfer participation and energy poverty incidences are jointly modeled. The empirical findings indicate that social transfer program participation reduces energy poverty. The negative association between energy poverty and social transfer program participation is more pronounced in urban areas compared with the rural areas.

Keywords: energy poverty, social transfers, panel data models, Turkey

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137 Modeling and Simulation of Vibratory Behavior of Hybrid Smart Composite Plate

Authors: Salah Aguib, Noureddine Chikh, Abdelmalek Khabli, Abdelkader Nour, Toufik Djedid, Lallia Kobzili

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This study presents the behavior of a hybrid smart sandwich plate with a magnetorheological elastomer core. In order to improve the vibrational behavior of the plate, the pseudo‐fibers formed by the effect of the magnetic field on the elastomer charged by the ferromagnetic particles are oriented at 45° with respect to the direction of the magnetic field at 0°. Ritz's approach is taken to solve the physical problem. In order to verify and compare the results obtained by the Ritz approach, an analysis using the finite element method was carried out. The rheological property of the MRE material at 0° and at 45° are determined experimentally, The studied elastomer is prepared by a mixture of silicone oil, RTV141A polymer, and 30% of iron particles of total mixture, the mixture obtained is mixed for about 15 minutes to obtain an elastomer paste with good homogenization. In order to develop a magnetorheological elastomer (MRE), this paste is injected into an aluminum mold and subjected to a magnetic field. In our work, we have chosen an ideal percentage of filling of 30%, to obtain the best characteristics of the MRE. The mechanical characteristics obtained by dynamic mechanical viscoanalyzer (DMA) are used in the two numerical approaches. The natural frequencies and the modal damping of the sandwich plate are calculated and discussed for various magnetic field intensities. The results obtained by the two methods are compared. These off‐axis anisotropic MRE structures could open up new opportunities in various fields of aeronautics, aerospace, mechanical engineering and civil engineering.

Keywords: hybrid smart sandwich plate, vibratory behavior, FEM, Ritz approach, MRE

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136 Analysis and Performance of European Geostationary Navigation Overlay Service System in North of Algeria for GPS Single Point Positioning

Authors: Tabti Lahouaria, Kahlouche Salem, Benadda Belkacem, Beldjilali Bilal

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The European Geostationary Navigation Overlay Service (EGNOS) provides an augmentation signal to GPS (Global Positioning System) single point positioning. Presently EGNOS provides data correction and integrity information using the GPS L1 (1575.42 MHz) frequency band. The main objective of this system is to provide a better real-time positioning precision than using GPS only. They are expected to be used with single-frequency code observations. EGNOS offers navigation performance for an open service (OS), in terms of precision and availability this performance gradually degrades as moving away from the service area. For accurate system performance, the service will become less and less available as the user moves away from the EGNOS service. The improvement in position solution is investigated using the two collocated dual frequency GPS, where no EGNOS Ranging and Integrity Monitoring Station (RIMS) exists. One of the pseudo-range was kept as GPS stand-alone and the other was corrected by EGNOS to estimate the planimetric and altimetric precision for different dates. It is found that precision in position improved significantly in the second due to EGNOS correction. The performance of EGNOS system in the north of Algeria is also investigated in terms of integrity. The results show that the horizontal protection level (HPL) value is below 18.25 meters (95%) and the vertical protection level (VPL) is below 42.22 meters (95 %). These results represent good integrity information transmitted by EGNOS for APV I service. This service is thus compliant with the aviation requirements for Approaches with Vertical Guidance (APV-I), which is characterised by 40 m HAL (horizontal alarm limit) and 50 m VAL (vertical alarm limit).

Keywords: EGNOS, GPS, positioning, integrity, protection level

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135 Development of Method for Recovery of Nickel from Aqueous Solution Using 2-Hydroxy-5-Nonyl- Acetophenone Oxime Impregnated on Activated Charcoal

Authors: A. O. Adebayo, G. A. Idowu, F. Odegbemi

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Investigations on the recovery of nickel from aqueous solution using 2-hydroxy-5-nonyl- acetophenone oxime (LIX-84I) impregnated on activated charcoal was carried out. The LIX-84I was impregnated onto the pores of dried activated charcoal by dry method and optimum conditions for different equilibrium parameters (pH, adsorbent dosage, extractant concentration, agitation time and temperature) were determined using a simulated solution of nickel. The kinetics and adsorption isotherm studies were also evaluated. It was observed that the efficiency of recovery with LIX-84I impregnated on charcoal was dependent on the pH of the aqueous solution as there was little or no recovery at pH below 4. However, as the pH was raised, percentage recovery increases and peaked at pH 5.0. The recovery was found to increase with temperature up to 60ºC. Also it was observed that nickel adsorbed onto the loaded charcoal best at a lower concentration (0.1M) of the extractant when compared with higher concentrations. Similarly, a moderately low dosage (1 g) of the adsorbent showed better recovery than larger dosages. These optimum conditions were used to recover nickel from the leachate of Ni-MH batteries dissolved with sulphuric acid, and a 99.6% recovery was attained. Adsorption isotherm studies showed that the equilibrium data fitted best to Temkin model, with a negative value of constant, b (-1.017 J/mol) and a high correlation coefficient, R² of 0.9913. Kinetic studies showed that the adsorption process followed a pseudo-second order model. Thermodynamic parameter values (∆G⁰, ∆H⁰, and ∆S⁰) showed that the adsorption was endothermic and spontaneous. The impregnated charcoal appreciably recovered nickel using a relatively smaller volume of extractant than what is required in solvent extraction. Desorption studies showed that the loaded charcoal is reusable for three times, and so might be economical for nickel recovery from waste battery.

Keywords: charcoal, impregnated, LIX-84I, nickel, recovery

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134 Partially Phosphorylated Polyvinyl Phosphate-PPVP Composite: Synthesis and Its Potentiality for Zr (IV) Extraction from an Acidic Medium

Authors: Khaled Alshamari

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Synthesized partially phosphorylated polyvinyl phosphate derivative (PPVP) was functionalized to extract Zirconium (IV) from Egyptian zircon sand. The specifications for the PPVP composite were approved effectively via different techniques, namely, FT-IR, XPS, BET, EDX, TGA, HNMR, C-NMR, GC-MS, XRD and ICP-OES analyses, which demonstrated a satisfactory synthesis of PPVP and zircon dissolution from Egyptian zircon sand. Factors controlling parameters, such as pH values, shaking time, initial zirconium concentration, PPVP dose, nitrate ions concentration, co-ions, temperature and eluting agents, have been optimized. At 25 ◦C, pH 0, 20 min shaking, 0.05 mol/L zirconium ions and 0.5 mol/L nitrate ions, PPVP has an exciting preservation potential of 195 mg/g, equivalent to 390 mg/L zirconium ions. From the extraction–distribution isotherm, the practical outcomes of Langmuir’s modeling are better than the Freundlich model, with a theoretical value of 196.07 mg/g, which is more in line with the experimental results of 195 mg/g. The zirconium ions adsorption onto the PPVP composite follows the pseudo-second-order kinetics with a theoretical capacity value of 204.08 mg/g. According to thermodynamic potential, the extraction process was expected to be an exothermic, spontaneous and beneficial extraction at low temperatures. The thermodynamic parameters ∆S (−0.03 kJ/mol), ∆H (−12.22 kJ/mol) and ∆G were also considered. As the temperature grows, ∆G values increase from −2.948 kJ/mol at 298 K to −1.941 kJ/mol at 338 K. Zirconium ions may be eluted from the working loaded PPVP by 0.025M HNO₃, with a 99% efficiency rate. It was found that zirconium ions revealed good separation factors towards some co-ions such as Hf⁴+ (28.82), Fe³+ (10.64), Ti⁴+ (28.82), V⁵+ (86.46) and U⁶+ (68.17). A successful alkali fusion technique with NaOH flux followed by the extraction with PPVP is used to obtain a high-purity zirconia concentrate with a zircon content of 72.77 % and a purity of 98.29%. As a result of this, the improved factors could finally be used.

Keywords: zirconium extraction, partially phosphorylated polyvinyl phosphate (PPVP), acidic medium, zircon

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133 Investigation of the Use of Surface-Modified Waste Orange Pulp for the Adsorption of Remazol Black B

Authors: Ceren Karaman, Onur Karaman

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The adsorption of Remazol Black B (RBB), an anionic dye, onto dried orange pulp (DOP) adsorbent prepared by only drying and by treating with cetyltrimetylammonium bromide (CTAB), a cationic surfactant, surface-modified orange pulp (SMOP) was studied in a stirred batch experiments system at 25°C. The adsorption of RBB on each adsorbent as a function of surfactant dosage, initial pH of the solution and initial dye concentration was investigated. The optimum amount of CTAB was found to be 25g/l. For RBB adsorption studies, while working pH value for the DOP adsorbent system was determined as 2.0, it was observed that this value shifted to 8.0 when the 25 g/l CTAB treated-orange pulp (SMOP) adsorbent was used. It was obtained that the adsorption rate and capacity increased to a certain value, and the adsorption efficiency decreased with increasing initial RBB concentration for both DOP and SMOP adsorbents at pH 2.0 and pH 8.0. While the highest adsorption capacity for DOP was determined as 62.4 mg/g at pH 2.0, and as 325.0 mg/g for SMOP at pH 8.0. As a result, it can be said that permanent cationic coating of the adsorbent surface by CTAB surfactant shifted the working pH from 2.0 to 8.0 and it increased the dye adsorption rate and capacity of orange pulp much more significantly at pH 8.0. The equilibrium RBB adsorption data on each adsorbent were best described by the Langmuir isotherm model. The adsorption kinetics of RBB on each adsorbent followed a pseudo-second-order model. Moreover, the intraparticle diffusion model was used to describe the kinetic data. It was found that diffusion is not the only rate controlling step. The adsorbent was characterized by the Brunauer–Emmett–Teller (BET) analysis, Fourier-transform-infrared (FTIR) spectroscopy, and scanning-electron-microscopy (SEM). The mechanism for the adsorption of RBB on the SMOP may include hydrophobic interaction, van der Waals interaction, stacking and electrostatic interaction.

Keywords: adsorption, Cetyltrimethylammonium Bromide (CTAB), orange pulp, Remazol Black B (RBB), surface modification

Procedia PDF Downloads 248
132 Gross Anatomical and Ultra Structural Microscopic Studies on the Nose of the Dromedary Camel (Camelus Dromederius)

Authors: Mahmoud S Gewaily, Atif Hasan, Mohamed Kassab, Ali A. Mansour

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The current study was carried out on the nose of seventeenth healthy adult camels. Specimens were collected from slaughter houses then fixed, dissected and photographed. For ultra structural studies, fresh samples were fixed in different fixatives and prepared for examination by light, scanning and electron microscopes. Grossly, nose of the camel had narrow nostrils, slit like in outline. In the nasal cavity, the nasal vestibule was narrow and has scanty dorsal and lateral cartilaginous support. The Nasal conchae (dorsal, middle and ventral) enclosed the dorsal, middle conchal sinuses and no ventral conchal sinus; instead there was recess and bull a. The ethmoidal conchae (8 in number) were noticeably fewer than in the other domestic animals like ox and horse. The olfactory mucosa was restricted to a small area covering the caudal parts of the ethmoidal conchae. The lining epithelium of the nasal cavity changes gradually from stratified squamous epithelium in the nasal vestibule to pseudo stratified columnar ciliated in the respiratory region and finally, olfactory epithelium covering the caudal parts of the ethmoidal conchae. In the dromedary camel, a special feature was the presence of dense and relatively long hair covering the nostrils and the rostral part of the nasal vestibule. In conclusion, the anatomical features of the nose of the dromedary camel, especially in its rostral parts enable this animal to breathe properly in the sandy dry weather.

Keywords: camel nose, anatomy, dromedary camel, nasal vestibule

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131 Electrospun Fibers Made from Biopolymers (Cellulose Acetate/Chitosan) for Metals Recovery

Authors: Mauricio Gómez, Esmeralda López, Ian Becar, Jaime Pizarro, Paula A. Zapata

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A biodegradable material is developed with adsorptive capacity for metals ion for intended use in mining tailings mitigating the environmental impact with economic retribution, two types of fibers were elaborated by electrospinning: (1) a cellulose acetate (CA) matrix and (2) a cellulose acetate (CA)/chitosan (CH) matrix evaluating the effect of CH in CA on its physicochemical properties. Through diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) the incorporation of chitosan in the matrix was identified, observing the band of the amino group at 1500 - 1600 [cm-1]. By scanning electron microscopy (SEM), Hg porosimetry, and CO2 isotherm at 273 [K], the intrafiber microporosity and interfiber macroporosity were identified, with an increase in the distribution of macropores for CA/CH fibers. In the tensile test, CH into the matrix produces a more ductile and tenacious behavior, where the % elongation at break increased by 33% with the other parameters constant. Thermal analysis by differential scanning calorimetry (DSC) and Thermogravimetric Analysis (TGA) showed that the incorporation of chitosan produces higher retention of water molecules due to the functional groups (amino groups (- NH3)), but there is a decrease in the specific heat and thermoplastic properties of the matrix since the glass transition temperature and softening temperature disappear. The effect of the optimum pH for CA and CA/CH fibers were studied in a batch system. In the adsorption kinetic study, the best isotherm model adapted to the experimental results corresponds to the Sips model and the kinetics corresponds to pseudo-second order

Keywords: environmental materials, wastewater treatment, electrospun fibers, biopolymers (cellulose acetate/chitosan), metals recovery

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130 Lithium Ion Supported on TiO2 Mixed Metal Oxides as a Heterogeneous Catalyst for Biodiesel Production from Canola Oil

Authors: Mariam Alsharifi, Hussein Znad, Ming Ang

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Considering the environmental issues and the shortage in the conventional fossil fuel sources, biodiesel has gained a promising solution to shift away from fossil based fuel as one of the sustainable and renewable energy. It is synthesized by transesterification of vegetable oils or animal fats with alcohol (methanol or ethanol) in the presence of a catalyst. This study focuses on synthesizing a high efficient Li/TiO2 heterogeneous catalyst for biodiesel production from canola oil. In this work, lithium immobilized onto TiO2 by the simple impregnation method. The catalyst was evaluated by transesterification reaction in a batch reactor under moderate reaction conditions. To study the effect of Li concentrations, a series of LiNO3 concentrations (20, 30, 40 wt. %) at different calcination temperatures (450, 600, 750 ºC) were evaluated. The Li/TiO2 catalysts are characterized by several spectroscopic and analytical techniques such as XRD, FT-IR, BET, TG-DSC and FESEM. The optimum values of impregnated Lithium nitrate on TiO2 and calcination temperature are 30 wt. % and 600 ºC, respectively, along with a high conversion to be 98 %. The XRD study revealed that the insertion of Li improved the catalyst efficiency without any alteration in structure of TiO2 The best performance of the catalyst was achieved when using a methanol to oil ratio of 24:1, 5 wt. % of catalyst loading, at 65◦C reaction temperature for 3 hours of reaction time. Moreover, the experimental kinetic data were compatible with the pseudo-first order model and the activation energy was (39.366) kJ/mol. The synthesized catalyst Li/TiO2 was applied to trans- esterify used cooking oil and exhibited a 91.73% conversion. The prepared catalyst has shown a high catalytic activity to produce biodiesel from fresh and used oil within mild reaction conditions.

Keywords: biodiesel, canola oil, environment, heterogeneous catalyst, impregnation method, renewable energy, transesterification

Procedia PDF Downloads 176
129 Direct-Displacement Based Design for Buildings with Non-Linear Viscous Dampers

Authors: Kelly F. Delgado-De Agrela, Sonia E. Ruiz, Marco A. Santos-Santiago

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An approach is proposed for the design of regular buildings equipped with non-linear viscous dissipating devices. The approach is based on a direct-displacement seismic design method which satisfies seismic performance objectives. The global system involved is formed by structural regular moment frames capable of supporting gravity and lateral loads with elastic response behavior plus a set of non-linear viscous dissipating devices which reduce the structural seismic response. The dampers are characterized by two design parameters: (1) a positive real exponent α which represents the non-linearity of the damper, and (2) the damping coefficient C of the device, whose constitutive force-velocity law is given by F=Cvᵃ, where v is the velocity between the ends of the damper. The procedure is carried out using a substitute structure. Two limits states are verified: serviceability and near collapse. The reduction of the spectral ordinates by the additional damping assumed in the design process and introduced to the structure by the viscous non-linear dampers is performed according to a damping reduction factor. For the design of the non-linear damper system, the real velocity is considered instead of the pseudo-velocity. The proposed design methodology is applied to an 8-story steel moment frame building equipped with non-linear viscous dampers, located in intermediate soil zone of Mexico City, with a dominant period Tₛ = 1s. In order to validate the approach, nonlinear static analyses and nonlinear time history analyses are performed.

Keywords: based design, direct-displacement based design, non-linear viscous dampers, performance design

Procedia PDF Downloads 193
128 A Rationale to Describe Ambident Reactivity

Authors: David Ryan, Martin Breugst, Turlough Downes, Peter A. Byrne, Gerard P. McGlacken

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An ambident nucleophile is a nucleophile that possesses two or more distinct nucleophilic sites that are linked through resonance and are effectively “in competition” for reaction with an electrophile. Examples include enolates, pyridone anions, and nitrite anions, among many others. Reactions of ambident nucleophiles and electrophiles are extremely prevalent at all levels of organic synthesis. The principle of hard and soft acids and bases (the “HSAB principle”) is most commonly cited in the explanation of selectivities in such reactions. Although this rationale is pervasive in any discussion on ambident reactivity, the HSAB principle has received considerable criticism. As a result, the principle’s supplantation has become an area of active interest in recent years. This project focuses on developing a model for rationalizing ambident reactivity. Presented here is an approach that incorporates computational calculations and experimental kinetic data to construct Gibbs energy profile diagrams. The preferred site of alkylation of nitrite anion with a range of ‘hard’ and ‘soft’ alkylating agents was established by ¹H NMR spectroscopy. Pseudo-first-order rate constants were measured directly by ¹H NMR reaction monitoring, and the corresponding second-order constants and Gibbs energies of activation were derived. These, in combination with computationally derived standard Gibbs energies of reaction, were sufficient to construct Gibbs energy wells. By representing the ambident system as a series of overlapping Gibbs energy wells, a more intuitive picture of ambident reactivity emerges. Here, previously unexplained switches in reactivity in reactions involving closely related electrophiles are elucidated.

Keywords: ambident, Gibbs, nucleophile, rates

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