Search results for: metals to polymers joining
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 2009

Search results for: metals to polymers joining

89 Development and application of Humidity-Responsive Controlled Release Active Packaging Based on Electrospinning Nanofibers and In Situ Growth Polymeric Film in Food preservation

Authors: Jin Yue

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Fresh produces especially fruits, vegetables, meats and aquatic products have limited shelf life and are highly susceptible to deterioration. Essential oils (EOs) extracted from plants have excellent antioxidant and broad-spectrum antibacterial activities, and they can play as natural food preservatives. But EOs are volatile, water insoluble, pungent, and easily decomposing under light and heat. Many approaches have been developed to improve the solubility and stability of EOs such as polymeric film, coating, nanoparticles, nano-emulsions and nanofibers. Construction of active packaging film which can incorporate EOs with high loading efficiency and controlled release of EOs has received great attention. It is still difficult to achieve accurate release of antibacterial compounds at specific target locations in active packaging. In this research, a relative humidity-responsive packaging material was designed, employing the electrospinning technique to fabricate a nanofibrous film loaded with a 4-terpineol/β-cyclodextrin inclusion complexes (4-TA/β-CD ICs). Functioning as an innovative food packaging material, the film demonstrated commendable attributes including pleasing appearance, thermal stability, mechanical properties, and effective barrier properties. The incorporation of inclusion complexes greatly enhanced the antioxidant and antibacterial activity of the film, particularly against Shewanella putrefaciens, with an inhibitory efficiency of up to 65%. Crucially, the film realized controlled release of 4-TA under 98% high relative humidity conditions by inducing the plasticization of polymers caused by water molecules, swelling of polymer chains, and destruction of hydrogen bonds within the cyclodextrin inclusion complex. This film with a long-term antimicrobial effect successfully extended the shelf life of Litopenaeus vannamei shrimp to 7 days at 4 °C. To further improve the loading efficiency and long-acting release of EOs, we synthesized the γ-cyclodextrin-metal organic frameworks (γ-CD-MOFs), and then efficiently anchored γ-CD-MOFs on chitosan-cellulose (CS-CEL) composite film by in situ growth method for controlled releasing of carvacrol (CAR). We found that the growth efficiency of γ-CD-MOFs was the highest when the concentration of CEL dispersion was 5%. The anchoring of γ-CD-MOFs on CS-CEL film significantly improved the surface area of CS-CEL film from 1.0294 m2/g to 43.3458 m2/g. The molecular docking and 1H NMR spectra indicated that γ-CD-MOF has better complexing and stabilizing ability for CAR molecules than γ-CD. In addition, the release of CAR reached 99.71±0.22% on the 10th day, while under 22% RH, the release pattern of CAR was a plateau with 14.71 ± 4.46%. The inhibition rate of this film against E. coli, S. aureus and B. cinerea was more than 99%, and extended the shelf life of strawberries to 7 days. By incorporating the merits of natural biopolymers and MOFs, this active packaging offers great potential as a substitute for traditional packaging materials.

Keywords: active packaging, antibacterial activity, controlled release, essential oils, food quality control

Procedia PDF Downloads 41
88 Synergy Surface Modification for High Performance Li-Rich Cathode

Authors: Aipeng Zhu, Yun Zhang

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The growing grievous environment problems together with the exhaustion of energy resources put urgent demands for developing high energy density. Considering the factors including capacity, resource and environment, Manganese-based lithium-rich layer-structured cathode materials xLi₂MnO₃⋅(1-x)LiMO₂ (M = Ni, Co, Mn, and other metals) are drawing increasing attention due to their high reversible capacities, high discharge potentials, and low cost. They are expected to be one type of the most promising cathode materials for the next-generation Li-ion batteries (LIBs) with higher energy densities. Unfortunately, their commercial applications are hindered with crucial drawbacks such as poor rate performance, limited cycle life and continuous falling of the discharge potential. With decades of extensive studies, significant achievements have been obtained in improving their cyclability and rate performances, but they cannot meet the requirement of commercial utilization till now. One major problem for lithium-rich layer-structured cathode materials (LLOs) is the side reaction during cycling, which leads to severe surface degradation. In this process, the metal ions can dissolve in the electrolyte, and the surface phase change can hinder the intercalation/deintercalation of Li ions and resulting in low capacity retention and low working voltage. To optimize the LLOs cathode material, the surface coating is an efficient method. Considering the price and stability, Al₂O₃ was used as a coating material in the research. Meanwhile, due to the low initial Coulombic efficiency (ICE), the pristine LLOs was pretreated by KMnO₄ to increase the ICE. The precursor was prepared by a facile coprecipitation method. The as-prepared precursor was then thoroughly mixed with Li₂CO₃ and calcined in air at 500℃ for 5h and 900℃ for 12h to produce Li₁.₂[Ni₀.₂Mn₀.₆]O₂ (LNMO). The LNMO was then put into 0.1ml/g KMnO₄ solution stirring for 3h. The resultant was filtered and washed with water, and dried in an oven. The LLOs obtained was dispersed in Al(NO₃)₃ solution. The mixture was lyophilized to confer the Al(NO₃)₃ was uniformly coated on LLOs. After lyophilization, the LLOs was calcined at 500℃ for 3h to obtain LNMO@LMO@ALO. The working electrodes were prepared by casting the mixture of active material, acetylene black, and binder (polyvinglidene fluoride) dissolved in N-methyl-2-pyrrolidone with a mass ratio of 80: 15: 5 onto an aluminum foil. The electrochemical performance tests showed that the multiple surface modified materials had a higher initial Coulombic efficiency (84%) and better capacity retention (91% after 100 cycles) compared with that of pristine LNMO (76% and 80%, respectively). The modified material suggests that the KMnO₄ pretreat and Al₂O₃ coating can increase the ICE and cycling stability.

Keywords: Li-rich materials, surface coating, lithium ion batteries, Al₂O₃

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87 Large-Scale Production of High-Performance Fiber-Metal-Laminates by Prepreg-Press-Technology

Authors: Christian Lauter, Corin Reuter, Shuang Wu, Thomas Troester

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Lightweight construction became more and more important over the last decades in several applications, e.g. in the automotive or aircraft sector. This is the result of economic and ecological constraints on the one hand and increasing safety and comfort requirements on the other hand. In the field of lightweight design, different approaches are used due to specific requirements towards the technical systems. The use of endless carbon fiber reinforced plastics (CFRP) offers the largest weight saving potential of sometimes more than 50% compared to conventional metal-constructions. However, there are very limited industrial applications because of the cost-intensive manufacturing of the fibers and production technologies. Other disadvantages of pure CFRP-structures affect the quality control or the damage resistance. One approach to meet these challenges is hybrid materials. This means CFRP and sheet metal are combined on a material level. Therefore, new opportunities for innovative process routes are realizable. Hybrid lightweight design results in lower costs due to an optimized material utilization and the possibility to integrate the structures in already existing production processes of automobile manufacturers. In recent and current research, the advantages of two-layered hybrid materials have been pointed out, i.e. the possibility to realize structures with tailored mechanical properties or to divide the curing cycle of the epoxy resin into two steps. Current research work at the Chair for Automotive Lightweight Design (LiA) at the Paderborn University focusses on production processes for fiber-metal-laminates. The aim of this work is the development and qualification of a large-scale production process for high-performance fiber-metal-laminates (FML) for industrial applications in the automotive or aircraft sector. Therefore, the prepreg-press-technology is used, in which pre-impregnated carbon fibers and sheet metals are formed and cured in a closed, heated mold. The investigations focus e.g. on the realization of short process chains and cycle times, on the reduction of time-consuming manual process steps, and the reduction of material costs. This paper gives an overview over the considerable steps of the production process in the beginning. Afterwards experimental results are discussed. This part concentrates on the influence of different process parameters on the mechanical properties, the laminate quality and the identification of process limits. Concluding the advantages of this technology compared to conventional FML-production-processes and other lightweight design approaches are carried out.

Keywords: composite material, fiber-metal-laminate, lightweight construction, prepreg-press-technology, large-series production

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86 Design and Development of Graphene Oxide Modified by Chitosan Nanosheets Showing pH-Sensitive Surface as a Smart Drug Delivery System for Control Release of Doxorubicin

Authors: Parisa Shirzadeh

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Drug delivery systems in which drugs are traditionally used, multi-stage and at specified intervals by patients, do not meet the needs of the world's up-to-date drug delivery. In today's world, we are dealing with a huge number of recombinant peptide and protean drugs and analogues of hormones in the body, most of which are made with genetic engineering techniques. Most of these drugs are used to treat critical diseases such as cancer. Due to the limitations of the traditional method, researchers sought to find ways to solve the problems of the traditional method to a large extent. Following these efforts, controlled drug release systems were introduced, which have many advantages. Using controlled release of the drug in the body, the concentration of the drug is kept at a certain level, and in a short time, it is done at a higher rate. Graphene is a natural material that is biodegradable, non-toxic, and natural compared to carbon nanotubes; its price is lower than carbon nanotubes and is cost-effective for industrialization. On the other hand, the presence of highly effective surfaces and wide surfaces of graphene plates makes it more effective to modify graphene than carbon nanotubes. Graphene oxide is often synthesized using concentrated oxidizers such as sulfuric acid, nitric acid, and potassium permanganate based on Hummer 1 method. In comparison with the initial graphene, the resulting graphene oxide is heavier and has carboxyl, hydroxyl, and epoxy groups. Therefore, graphene oxide is very hydrophilic and easily dissolves in water and creates a stable solution. On the other hand, because the hydroxyl, carboxyl, and epoxy groups created on the surface are highly reactive, they have the ability to work with other functional groups such as amines, esters, polymers, etc. Connect and bring new features to the surface of graphene. In fact, it can be concluded that the creation of hydroxyl groups, Carboxyl, and epoxy and in fact graphene oxidation is the first step and step in creating other functional groups on the surface of graphene. Chitosan is a natural polymer and does not cause toxicity in the body. Due to its chemical structure and having OH and NH groups, it is suitable for binding to graphene oxide and increasing its solubility in aqueous solutions. Graphene oxide (GO) has been modified by chitosan (CS) covalently, developed for control release of doxorubicin (DOX). In this study, GO is produced by the hummer method under acidic conditions. Then, it is chlorinated by oxalyl chloride to increase its reactivity against amine. After that, in the presence of chitosan, the amino reaction was performed to form amide transplantation, and the doxorubicin was connected to the carrier surface by π-π interaction in buffer phosphate. GO, GO-CS, and GO-CS-DOX characterized by FT-IR, RAMAN, TGA, and SEM. The ability to load and release is determined by UV-Visible spectroscopy. The loading result showed a high capacity of DOX absorption (99%) and pH dependence identified as a result of DOX release from GO-CS nanosheet at pH 5.3 and 7.4, which show a fast release rate in acidic conditions.

Keywords: graphene oxide, chitosan, nanosheet, controlled drug release, doxorubicin

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85 Willingness to Pay for Improvements of MSW Disposal: Views from Online Survey

Authors: Amornchai Challcharoenwattana, Chanathip Pharino

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Rising amount of MSW every day, maximizing material diversions from landfills via recycling is a prefer method to land dumping. Characteristic of Thai MSW is classified as 40 -60 per cent compostable wastes while potentially recyclable materials in waste streams are composed of plastics, papers, glasses, and metals. However, rate of material recovery from MSW, excluding composting or biogas generation, in Thailand is still low. Thailand’s recycling rate in 2010 was only 20.5 per cent. Central government as well as local governments in Thailand have tried to curb this problem by charging some of MSW management fees at the users. However, the fee is often too low to promote MSW minimization. The objective of this paper is to identify levels of willingness-to-pay (WTP) for MSW recycling in different social structures with expected outcome of sustainable MSW managements for different town settlements to maximize MSW recycling pertaining to each town’s potential. The method of eliciting WTP is a payment card. The questionnaire was deployed using online survey during December 2012. Responses were categorized into respondents living in Bangkok, living in other municipality areas, or outside municipality area. The responses were analysed using descriptive statistics, and multiple linear regression analysis to identify relationships and factors that could influence high or low WTP. During the survey period, there were 168 filled questionnaires from total 689 visits. However, only 96 questionnaires could be usable. Among respondents in the usable questionnaires, 36 respondents lived in within the boundary of Bangkok Metropolitan Administration while 45 respondents lived in the chartered areas that were classified as other municipality but not in BMA. Most of respondents were well-off as 75 respondents reported positive monthly cash flow (77.32%), 15 respondents reported neutral monthly cash flow (15.46%) while 7 respondent reported negative monthly cash flow (7.22%). For WTP data including WTP of 0 baht with valid responses, ranking from the highest means of WTP to the lowest WTP of respondents by geographical locations for good MSW management were Bangkok (196 baht/month), municipalities (154 baht/month), and non-urbanized towns (111 baht/month). In-depth analysis was conducted to analyse whether there are additional room for further increase of MSW management fees from the current payment that each correspondent is currently paying. The result from multiple-regression analysis suggested that the following factors could impacts the increase or decrease of WTP: incomes, age, and gender. Overall, the outcome of this study suggests that survey respondents are likely to support improvement of MSW treatments that are not solely relying on landfilling technique. Recommendations for further studies are to obtain larger sample sizes in order to improve statistical powers and to provide better accuracy of WTP study.

Keywords: MSW, willingness to pay, payment card, waste seperation

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84 Upgrading of Bio-Oil by Bio-Pd Catalyst

Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

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This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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83 Erosion and Deposition of Terrestrial Soil Supplies Nutrients to Estuaries and Coastal Bays: A Flood Simulation Study of Sediment-Nutrient Flux

Authors: Kaitlyn O'Mara, Michele Burford

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Estuaries and coastal bays can receive large quantities of sediment from surrounding catchments during flooding or high flow periods. Large river systems that feed freshwater into estuaries can flow through several catchments of varying geology. Human modification of catchments for agriculture, industry and urban use can contaminate soils with excess nutrients, trace metals and other pollutants. Land clearing, especially clearing of riparian vegetation, can accelerate erosion, mobilising, transporting and depositing soil particles into rivers, estuaries and coastal bays. In this study, a flood simulation experiment was used to study the flux of nutrients between soil particles and water during this erosion, transport and deposition process. Granite, sedimentary and basalt surface soils (as well as sub-soils of granite and sedimentary) were collected from eroding areas surrounding the Brisbane River, Australia. The <63 µm size fraction of each soil type was tumbled in freshwater for 3 days, to simulation flood erosion and transport, followed by stationary exposure to seawater for 4 weeks, to simulate deposition into estuaries. Filtered water samples were taken at multiple time points throughout the experiment and analysed for water nutrient concentrations. The highest rates of nutrient release occurred during the first hour of exposure to freshwater and seawater, indicating a chemical reaction with seawater that may act to release some nutrient particles that remain bound to the soil during turbulent freshwater transport. Although released at a slower rate than the first hour, all of the surface soil types showed continual ammonia, nitrite and nitrate release over the 4-week seawater exposure, suggesting that these soils may provide ongoing supply of these nutrients to estuarine waters after deposition. Basalt surface soil released the highest concentrations of phosphates and dissolved organic phosphorus. Basalt soils are found in much of the agricultural land surrounding the Brisbane River and contributed largely to the 2011 Brisbane River flood plume deposit in Moreton Bay, suggesting these soils may be a source of phosphate enrichment in the bay. The results of this study suggest that erosion of catchment soils during storm and flood events may be a source of nutrient supply in receiving waterways, both freshwater and marine, and that the amount of nutrient release following these events may be affected by the type of soil deposited. For example, flooding in different catchments of a river system over time may result in different algal and food web responses in receiving estuaries.

Keywords: flood, nitrogen, nutrient, phosphorus, sediment, soil

Procedia PDF Downloads 157
82 Ways to Prevent Increased Wear of the Drive Box Parts and the Central Drive of the Civil Aviation Turbo Engine Based on Tribology

Authors: Liudmila Shabalinskaya, Victor Golovanov, Liudmila Milinis, Sergey Loponos, Alexander Maslov, D. O. Frolov

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The work is devoted to the rapid laboratory diagnosis of the condition of aircraft friction units, based on the application of the nondestructive testing method by analyzing the parameters of wear particles, or tribodiagnostics. The most important task of tribodiagnostics is to develop recommendations for the selection of more advanced designs, materials and lubricants based on data on wear processes for increasing the life and ensuring the safety of the operation of machines and mechanisms. The object of tribodiagnostics in this work are the tooth gears of the central drive and the gearboxes of the gas turbine engine of the civil aviation PS-90A type, in which rolling friction and sliding friction with slip occur. The main criterion for evaluating the technical state of lubricated friction units of a gas turbine engine is the intensity and rate of wear of the friction surfaces of the friction unit parts. When the engine is running, oil samples are taken and the state of the friction surfaces is evaluated according to the parameters of the wear particles contained in the oil sample, which carry important and detailed information about the wear processes in the engine transmission units. The parameters carrying this information include the concentration of wear particles and metals in the oil, the dispersion composition, the shape, the size ratio and the number of particles, the state of their surfaces, the presence in the oil of various mechanical impurities of non-metallic origin. Such a morphological analysis of wear particles has been introduced into the order of monitoring the status and diagnostics of various aircraft engines, including a gas turbine engine, since the type of wear characteristic of the central drive and the drive box is surface fatigue wear and the beginning of its development, accompanied by the formation of microcracks, leads to the formation of spherical, up to 10 μm in size, and in the aftermath of flocculent particles measuring 20-200 μm in size. Tribodiagnostics using the morphological analysis of wear particles includes the following techniques: ferrography, filtering, and computer analysis of the classification and counting of wear particles. Based on the analysis of several series of oil samples taken from the drive box of the engine during their operating time, a study was carried out of the processes of wear kinetics. Based on the results of the study and comparing the series of criteria for tribodiagnostics, wear state ratings and statistics of the results of morphological analysis, norms for the normal operating regime were developed. The study allowed to develop levels of wear state for friction surfaces of gearing and a 10-point rating system for estimating the likelihood of the occurrence of an increased wear mode and, accordingly, prevention of engine failures in flight.

Keywords: aviation, box of drives, morphological analysis, tribodiagnostics, tribology, ferrography, filtering, wear particle

Procedia PDF Downloads 238
81 Valorization of Banana Peels for Mercury Removal in Environmental Realist Conditions

Authors: E. Fabre, C. Vale, E. Pereira, C. M. Silva

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Introduction: Mercury is one of the most troublesome toxic metals responsible for the contamination of the aquatic systems due to its accumulation and bioamplification along the food chain. The 2030 agenda for sustainable development of United Nations promotes the improving of water quality by reducing water pollution and foments an enhance in wastewater treatment, encouraging their recycling and safe water reuse globally. Sorption processes are widely used in wastewater treatments due to their many advantages such as high efficiency and low operational costs. In these processes the target contaminant is removed from the solution by a solid sorbent. The more selective and low cost is the biosorbent the more attractive becomes the process. Agricultural wastes are especially attractive approaches for sorption. They are largely available, have no commercial value and require little or no processing. In this work, banana peels were tested for mercury removal from low concentrated solutions. In order to investigate the applicability of this solid, six water matrices were used increasing the complexity from natural waters to a real wastewater. Studies of kinetics and equilibrium were also performed using the most known models to evaluate the viability of the process In line with the concept of circular economy, this study adds value to this by-product as well as contributes to liquid waste management. Experimental: The solutions were prepared with Hg(II) initial concentration of 50 µg L-1 in natural waters, at 22 ± 1 ºC, pH 6, magnetically stirring at 650 rpm and biosorbent mass of 0.5 g L-1. NaCl was added to obtain the salt solutions, seawater was collected from the Portuguese coast and the real wastewater was kindly provided by ISQ - Instituto de Soldadura e qualidade (Welding and Quality Institute) and diluted until the same concentration of 50 µg L-1. Banana peels were previously freeze-drying, milled, sieved and the particles < 1 mm were used. Results: Banana peels removed more than 90% of Hg(II) from all the synthetic solutions studied. In these cases, the enhance in the complexity of the water type promoted a higher mercury removal. In salt waters, the biosorbent showed removals of 96%, 95% and 98 % for 3, 15 and 30 g L-1 of NaCl, respectively. The residual concentration of Hg(II) in solution achieved the level of drinking water regulation (1 µg L-1). For real matrices, the lower Hg(II) elimination (93 % for seawater and 81 % for the real wastewaters), can be explained by the competition between the Hg(II) ions and the other elements present in these solutions for the sorption sites. Regarding the equilibrium study, the experimental data are better described by the Freundlich isotherm (R ^ 2=0.991). The Elovich equation provided the best fit to the kinetic points. Conclusions: The results exhibited the great ability of the banana peels to remove mercury. The environmental realist conditions studied in this work, highlight their potential usage as biosorbents in water remediation processes.

Keywords: banana peels, mercury removal, sorption, water treatment

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80 The Effect of TiO₂ Nanoparticles on Zebrafish Embryos

Authors: Elena Maria Scalisi

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Currently, photodegradation by nanoparticles (NPs) is a common solution for wastewater treatment. Nanoparticles are efficient for removing organic and inorganic pollutants, heavy metals from wastewater and killing microorganisms through environmentally friendly. In this context, the major representative of photocatalytic technology for industrial wastewater treatment are TiO₂ nanoparticles (TiO₂-NPs). TiO₂-NPs have a strong catalytic activity that depends to their physicochemical properties. Thanks to their small size (between 1-100 nm), nanoparticles occupy less volume, then their surface area increases. The increase in the surface-to-volume ratio results in the increase of the particle surface energy, which improve their reactivity potential. However, these unique properties represent risks to the ecosystems and organisms when unintentionally TiO₂-NPs are release into the environment and absorbed by living organisms. Several studies confirm that there is a high level of interest concerning the safety of TiO₂-NPs in the aquatic environment, furthermore, ecotoxicological tools are useful to correctly evaluate their toxicity. In the current study, we aimed to characterize potential toxic effects of TiO₂-NP suspension to zebrafish during embryo-larval stages to evaluate parameters such as survival rates, malformation, hatching, the overall length of the larvae heartbeat, and biochemical biomarkers that reflect the acute toxicity and sublethal effects of TiO₂-NPs. Zebrafish embryos were exposed to titanium dioxide nanoparticles (TiO₂-NPs at 1mg/L, 2mg/L, and 4mg/L) from fertilization to the free swimming stage (144hpf). Every day, we recorded the toxicological endpoints, moreover, immunohistochemical analysis has been performed at the end of the exposure. In particular, we have evaluate the expression of the following biomarkers: Heat Shock Protein 70 (HSP70), Poly ADP-Ribose Polymerase-1 (PARP-1), Metallothioneins (MTs). Our results have shown that hatch ability, survival, and malformation rate were not affected by TiO₂ NPs at these exposure levels. However, TiO₂-NPs caused an increase of heartbeat and reduction of body length; at the same time, TiO₂-NPs have inducted the production of ROS and the expression of oxidative stress biomarkers HSP70 and PARP-1. Hight positivity for PARP-1 at all concentration tested was observed. As regards MT, positivity was found in the expression of this biomarker in the whole body of the embryo, with the exception of the end of the tail. Metallothioneins (MT) are biomarkers widely used in environmental monitoring programs for aquatic creatures. At the light of our results i.e. no death until the end of the experiment (144hpf), no malformation and expression of the biomarkers mentioned, it is evident that zebrafish larvae with their natural detoxification pathways are able to resist the presence of toxic substances and then they can tolerate the presence of metal concentrations. However, an excessive oxidative state can compromise cell function, therefore the uncontrolled release of nanoparticles into the environment is severe and must be constantly monitored.

Keywords: nanoparticles, embryo zebrafish, HSP70, PARP-1

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79 Effect of Oxygen Ion Irradiation on the Structural, Spectral and Optical Properties of L-Arginine Acetate Single Crystals

Authors: N. Renuka, R. Ramesh Babu, N. Vijayan

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Ion beams play a significant role in the process of tuning the properties of materials. Based on the radiation behavior, the engineering materials are categorized into two different types. The first one comprises organic solids which are sensitive to the energy deposited in their electronic system and the second one comprises metals which are insensitive to the energy deposited in their electronic system. However, exposure to swift heavy ions alters this general behavior. Depending on the mass, kinetic energy and nuclear charge, an ion can produce modifications within a thin surface layer or it can penetrate deeply to produce long and narrow distorted area along its path. When a high energetic ion beam impinges on a material, it causes two different types of changes in the material due to the columbic interaction between the target atom and the energetic ion beam: (i) inelastic collisions of the energetic ion with the atomic electrons of the material; and (ii) elastic scattering from the nuclei of the atoms of the material, which is extremely responsible for relocating the atoms of matter from their lattice position. The exposure of the heavy ions renders the material return to equilibrium state during which the material undergoes surface and bulk modifications which depends on the mass of the projectile ion, physical properties of the target material, its energy, and beam dimension. It is well established that electronic stopping power plays a major role in the defect creation mechanism provided it exceeds a threshold which strongly depends on the nature of the target material. There are reports available on heavy ion irradiation especially on crystalline materials to tune their physical and chemical properties. L-Arginine Acetate [LAA] is a potential semi-organic nonlinear optical crystal and its optical, mechanical and thermal properties have already been reported The main objective of the present work is to enhance or tune the structural and optical properties of LAA single crystals by heavy ion irradiation. In the present study, a potential nonlinear optical single crystal, L-arginine acetate (LAA) was grown by slow evaporation solution growth technique. The grown LAA single crystal was irradiated with oxygen ions at the dose rate of 600 krad and 1M rad in order to tune the structural and optical properties. The structural properties of pristine and oxygen ions irradiated LAA single crystals were studied using Powder X- ray diffraction and Fourier Transform Infrared spectral studies which reveal the structural changes that are generated due to irradiation. Optical behavior of pristine and oxygen ions irradiated crystals is studied by UV-Vis-NIR and photoluminescence analyses. From this investigation we can concluded that oxygen ions irradiation modifies the structural and optical properties of LAA single crystals.

Keywords: heavy ion irradiation, NLO single crystal, photoluminescence, X-ray diffractometer

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78 Precursor Synthesis of Carbon Materials with Different Aggregates Morphologies

Authors: Nikolai A. Khlebnikov, Vladimir N. Krasilnikov, Evgenii V. Polyakov, Anastasia A. Maltceva

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Carbon materials with advanced surfaces are widely used both in modern industry and in environmental protection. The physical-chemical nature of these materials is determined by the morphology of primary atomic and molecular carbon structures, which are the basis for synthesizing the following materials: zero-dimensional (fullerenes), one-dimensional (fiber, tubes), two-dimensional (graphene) carbon nanostructures, three-dimensional (multi-layer graphene, graphite, foams) with unique physical-chemical and functional properties. Experience shows that the microscopic morphological level is the basis for the creation of the next mesoscopic morphological level. The dependence of the morphology on the chemical way and process prehistory (crystallization, colloids formation, liquid crystal state and other) is the peculiarity of the last called level. These factors determine the consumer properties of carbon materials, such as specific surface area, porosity, chemical resistance in corrosive environments, catalytic and adsorption activities. Based on the developed ideology of thin precursor synthesis, the authors discuss one of the approaches of the porosity control of carbon-containing materials with a given aggregates morphology. The low-temperature thermolysis of precursors in a gas environment of a given composition is the basis of the above-mentioned idea. The processes of carbothermic precursor synthesis of two different compounds: tungsten carbide WC:nC and zinc oxide ZnO:nC containing an impurity phase in the form of free carbon were selected as subjects of the research. In the first case, the transition metal (tungsten) forming carbides was the object of the synthesis. In the second case, there was selected zinc that does not form carbides. The synthesis of both kinds of transition metals compounds was conducted by the method of precursor carbothermic synthesis from the organic solution. ZnO:nC composites were obtained by thermolysis of succinate Zn(OO(CH2)2OO), formate glycolate Zn(HCOO)(OCH2CH2O)1/2, glycerolate Zn(OCH2CHOCH2OH), and tartrate Zn(OOCCH(OH)CH(OH)COO). WC:nC composite was synthesized from ammonium paratungstate and glycerol. In all cases, carbon structures that are specific for diamond- like carbon forms appeared on the surface of WC and ZnO particles after the heat treatment. Tungsten carbide and zinc oxide were removed from the composites by selective chemical dissolution preserving the amorphous carbon phase. This work presents the results of investigating WC:nC and ZnO:nC composites and carbon nanopowders with tubular, tape, plate and onion morphologies of aggregates that are separated by chemical dissolution of WC and ZnO from the composites by the following methods: SEM, TEM, XPA, Raman spectroscopy, and BET. The connection between the carbon morphology under the conditions of synthesis and chemical nature of the precursor and the possibility of regulation of the morphology with the specific surface area up to 1700-2000 m2/g of carbon-structured materials are discussed.

Keywords: carbon morphology, composite materials, precursor synthesis, tungsten carbide, zinc oxide

Procedia PDF Downloads 306
77 A Robust Stretchable Bio Micro-Electromechanical Systems Technology for High-Strain in vitro Cellular Studies

Authors: Tiffany Baetens, Sophie Halliez, Luc Buée, Emiliano Pallecchi, Vincent Thomy, Steve Arscott

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We demonstrate here a viable stretchable bio-microelectromechanical systems (BioMEMS) technology for use with biological studies concerned with the effect of high mechanical strains on living cells. An example of this is traumatic brain injury (TBI) where neurons are damaged with physical force to the brain during, e.g., accidents and sports. Robust, miniaturized integrated systems are needed by biologists to be able to study the effect of TBI on neuron cells in vitro. The major challenges in this area are (i) to develop micro, and nanofabrication processes which are based on stretchable substrates and to (ii) create systems which are robust and performant at very high mechanical strain values—sometimes as high as 100%. At the time of writing, such processes and systems were rapidly evolving subject of research and development. The BioMEMS which we present here is composed of an elastomer substrate (low Young’s modulus ~1 MPa) onto which is patterned robust electrodes and insulators. The patterning of the thin films is achieved using standard photolithography techniques directly on the elastomer substrate—thus making the process generic and applicable to many materials’ in based systems. The chosen elastomer used is commercial ‘Sylgard 184’ polydimethylsiloxane (PDMS). It is spin-coated onto a silicon wafer. Multistep ultra-violet based photolithography involving commercial photoresists are then used to pattern robust thin film metallic electrodes (chromium/gold) and insulating layers (parylene) on the top of the PDMS substrate. The thin film metals are deposited using thermal evaporation and shaped using lift-off techniques The BioMEMS has been characterized mechanically using an in-house strain-applicator tool. The system is composed of 12 electrodes with one reference electrode transversally-orientated to the uniaxial longitudinal straining of the system. The electrical resistance of the electrodes is observed to remain very stable with applied strain—with a resistivity approaching that of evaporated gold—up to an interline strain of ~50%. The mechanical characterization revealed some interesting original properties of such stretchable BioMEMS. For example, a Poisson effect induced electrical ‘self-healing’ of cracking was identified. Biocompatibility of the commercial photoresist has been studied and is conclusive. We will present the results of the BioMEMS, which has also characterized living cells with a commercial Multi Electrode Array (MEA) characterization tool (Multi Channel Systems, USA). The BioMEMS enables the cells to be strained up to 50% and then characterized electrically and optically.

Keywords: BioMEMS, elastomer, electrical impedance measurements of living cells, high mechanical strain, microfabrication, stretchable systems, thin films, traumatic brain injury

Procedia PDF Downloads 127
76 Dynamic-cognition of Strategic Mineral Commodities; An Empirical Assessment

Authors: Carlos Tapia Cortez, Serkan Saydam, Jeff Coulton, Claude Sammut

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Strategic mineral commodities (SMC) both energetic and metals have long been fundamental for human beings. There is a strong and long-run relation between the mineral resources industry and society's evolution, with the provision of primary raw materials, becoming one of the most significant drivers of economic growth. Due to mineral resources’ relevance for the entire economy and society, an understanding of the SMC market behaviour to simulate price fluctuations has become crucial for governments and firms. For any human activity, SMC price fluctuations are affected by economic, geopolitical, environmental, technological and psychological issues, where cognition has a major role. Cognition is defined as the capacity to store information in memory, processing and decision making for problem-solving or human adaptation. Thus, it has a significant role in those systems that exhibit dynamic equilibrium through time, such as economic growth. Cognition allows not only understanding past behaviours and trends in SCM markets but also supports future expectations of demand/supply levels and prices, although speculations are unavoidable. Technological developments may also be defined as a cognitive system. Since the Industrial Revolution, technological developments have had a significant influence on SMC production costs and prices, likewise allowing co-integration between commodities and market locations. It suggests a close relation between structural breaks, technology and prices evolution. SCM prices forecasting have been commonly addressed by econometrics and Gaussian-probabilistic models. Econometrics models may incorporate the relationship between variables; however, they are statics that leads to an incomplete approach of prices evolution through time. Gaussian-probabilistic models may evolve through time; however, price fluctuations are addressed by the assumption of random behaviour and normal distribution which seems to be far from the real behaviour of both market and prices. Random fluctuation ignores the evolution of market events and the technical and temporal relation between variables, giving the illusion of controlled future events. Normal distribution underestimates price fluctuations by using restricted ranges, curtailing decisions making into a pre-established space. A proper understanding of SMC's price dynamics taking into account the historical-cognitive relation between economic, technological and psychological factors over time is fundamental in attempting to simulate prices. The aim of this paper is to discuss the SMC market cognition hypothesis and empirically demonstrate its dynamic-cognitive capacity. Three of the largest and traded SMC's: oil, copper and gold, will be assessed to examine the economic, technological and psychological cognition respectively.

Keywords: commodity price simulation, commodity price uncertainties, dynamic-cognition, dynamic systems

Procedia PDF Downloads 436
75 Integration of a Protective Film to Enhance the Longevity and Performance of Miniaturized Ion Sensors

Authors: Antonio Ruiz Gonzalez, Kwang-Leong Choy

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The measurement of electrolytes has a high value in the clinical routine. Ions are present in all body fluids with variable concentrations and are involved in multiple pathologies such as heart failures and chronic kidney disease. In the case of dissolved potassium, although a high concentration in the blood (hyperkalemia) is relatively uncommon in the general population, it is one of the most frequent acute electrolyte abnormalities. In recent years, the integration of thin films technologies in this field has allowed the development of highly sensitive biosensors with ultra-low limits of detection for the assessment of metals in liquid samples. However, despite the current efforts in the miniaturization of sensitive devices and their integration into portable systems, only a limited number of successful examples used commercially can be found. This fact can be attributed to a high cost involved in their production and the sustained degradation of the electrodes over time, which causes a signal drift in the measurements. Thus, there is an unmet necessity for the development of low-cost and robust sensors for the real-time monitoring of analyte concentrations in patients to allow the early detection and diagnosis of diseases. This paper reports a thin film ion-selective sensor for the evaluation of potassium ions in aqueous samples. As an alternative for this fabrication method, aerosol assisted chemical vapor deposition (AACVD), was applied due to cost-effectivity and fine control over the film deposition. Such a technique does not require vacuum and is suitable for the coating of large surface areas and structures with complex geometries. This approach allowed the fabrication of highly homogeneous surfaces with well-defined microstructures onto 50 nm thin gold layers. The degradative processes of the ubiquitously employed poly (vinyl chloride) membranes in contact with an electrolyte solution were studied, including the polymer leaching process, mechanical desorption of nanoparticles and chemical degradation over time. Rational design of a protective coating based on an organosilicon material in combination with cellulose to improve the long-term stability of the sensors was then carried out, showing an improvement in the performance after 5 weeks. The antifouling properties of such coating were assessed using a cutting-edge quartz microbalance sensor, allowing the quantification of the adsorbed proteins in the nanogram range. A correlation between the microstructural properties of the films with the surface energy and biomolecules adhesion was then found and used to optimize the protective film.

Keywords: hyperkalemia, drift, AACVD, organosilicon

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74 Growth and Differentiation of Mesenchymal Stem Cells on Titanium Alloy Ti6Al4V and Novel Beta Titanium Alloy Ti36Nb6Ta

Authors: Eva Filová, Jana Daňková, Věra Sovková, Matej Daniel

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Titanium alloys are biocompatible metals that are widely used in clinical practice as load bearing implants. The chemical modification may influence cell adhesion, proliferation, and differentiation as well as stiffness of the material. The aim of the study was to evaluate the adhesion, growth and differentiation of pig mesenchymal stem cells on the novel beta titanium alloy Ti36Nb6Ta compared to standard medical titanium alloy Ti6Al4V. Discs of Ti36Nb6Ta and Ti6Al4V alloy were sterilized by ethanol, put in 48-well plates, and seeded by pig mesenchymal stem cells at the density of 60×103/cm2 and cultured in Minimum essential medium (Sigma) supplemented with 10% fetal bovine serum and penicillin/streptomycin. Cell viability was evaluated using MTS assay (CellTiter 96® AQueous One Solution Cell Proliferation Assay;Promega), cell proliferation using Quant-iT™ ds DNA Assay Kit (Life Technologies). Cells were stained immunohistochemically using monoclonal antibody beta-actin, and secondary antibody conjugated with AlexaFluor®488 and subsequently the spread area of cells was measured. Cell differentiation was evaluated by alkaline phosphatase assay using p-nitrophenyl phosphate (pNPP) as a substrate; the reaction was stopped by NaOH, and the absorbance was measured at 405 nm. Osteocalcin, specific bone marker was stained immunohistochemically and subsequently visualized using confocal microscopy; the fluorescence intensity was analyzed and quantified. Moreover, gene expression of osteogenic markers osteocalcin and type I collagen was evaluated by real-time reverse transcription-PCR (qRT-PCR). For statistical evaluation, One-way ANOVA followed by Student-Newman-Keuls Method was used. For qRT-PCR, the nonparametric Kruskal-Wallis Test and Dunn's Multiple Comparison Test were used. The absorbance in MTS assay was significantly higher on titanium alloy Ti6Al4V compared to beta titanium alloy Ti36Nb6Ta on days 7 and 14. Mesenchymal stem cells were well spread on both alloys, but no difference in spread area was found. No differences in alkaline phosphatase assay, fluorescence intensity of osteocalcin as well as the expression of type I collagen, and osteocalcin genes were observed. Higher expression of type I collagen compared to osteocalcin was observed for cells on both alloys. Both beta titanium alloy Ti36Nb6Ta and titanium alloy Ti6Al4V Ti36Nb6Ta supported mesenchymal stem cellsˈ adhesion, proliferation and osteogenic differentiation. Novel beta titanium alloys Ti36Nb6Ta is a promising material for bone implantation. The project was supported by the Czech Science Foundation: grant No. 16-14758S, the Grant Agency of the Charles University, grant No. 1246314 and by the Ministry of Education, Youth and Sports NPU I: LO1309.

Keywords: beta titanium, cell growth, mesenchymal stem cells, titanium alloy, implant

Procedia PDF Downloads 296
73 Fractional, Component and Morphological Composition of Ambient Air Dust in the Areas of Mining Industry

Authors: S.V. Kleyn, S.Yu. Zagorodnov, А.А. Kokoulina

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Technogenic emissions of the mining and processing complex are characterized by a high content of chemical components and solid dust particles. However, each industrial enterprise and the surrounding area have features that require refinement and parameterization. Numerous studies have shown the negative impact of fine dust PM10 and PM2.5 on the health, as well as the possibility of toxic components absorption, including heavy metals by dust particles. The target of the study was the quantitative assessment of the fractional and particle size composition of ambient air dust in the area of impact by primary magnesium production complex. Also, we tried to describe the morphology features of dust particles. Study methods. To identify the dust emission sources, the analysis of the production process has been carried out. The particulate composition of the emissions was measured using laser particle analyzer Microtrac S3500 (covered range of particle size is 20 nm to 2000 km). Particle morphology and the component composition were established by electron microscopy by scanning microscope of high resolution (magnification rate - 5 to 300 000 times) with X-ray fluorescence device S3400N ‘HITACHI’. The chemical composition was identified by X-ray analysis of the samples using an X-ray diffractometer XRD-700 ‘Shimadzu’. Determination of the dust pollution level was carried out using model calculations of emissions in the atmosphere dispersion. The calculations were verified by instrumental studies. Results of the study. The results demonstrated that the dust emissions of different technical processes are heterogeneous and fractional structure is complicated. The percentage of particle sizes up to 2.5 micrometres inclusive was ranged from 0.00 to 56.70%; particle sizes less than 10 microns inclusive – 0.00 - 85.60%; particle sizes greater than 10 microns - 14.40% -100.00%. During microscopy, the presence of nanoscale size particles has been detected. Studied dust particles are round, irregular, cubic and integral shapes. The composition of the dust includes magnesium, sodium, potassium, calcium, iron, chlorine. On the base of obtained results, it was performed the model calculations of dust emissions dispersion and establishment of the areas of fine dust РМ 10 and РМ 2.5 distribution. It was found that the dust emissions of fine powder fractions PM10 and PM2.5 are dispersed over large distances and beyond the border of the industrial site of the enterprise. The population living near the enterprise is exposed to the risk of diseases associated with dust exposure. Data are transferred to the economic entity to make decisions on the measures to minimize the risks. Exposure and risks indicators on the health are used to provide named patient health and preventive care to the citizens living in the area of negative impact of the facility.

Keywords: dust emissions, еxposure assessment, PM 10, PM 2.5

Procedia PDF Downloads 239
72 Formulation of Lipid-Based Tableted Spray-Congealed Microparticles for Zero Order Release of Vildagliptin

Authors: Hend Ben Tkhayat , Khaled Al Zahabi, Husam Younes

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Introduction: Vildagliptin (VG), a dipeptidyl peptidase-4 inhibitor (DPP-4), was proven to be an active agent for the treatment of type 2 diabetes. VG works by enhancing and prolonging the activity of incretins which improves insulin secretion and decreases glucagon release, therefore lowering blood glucose level. It is usually used with various classes, such as insulin sensitizers or metformin. VG is currently only marketed as an immediate-release tablet that is administered twice daily. In this project, we aim to formulate an extended-release with a zero-order profile tableted lipid microparticles of VG that could be administered once daily ensuring the patient’s convenience. Method: The spray-congealing technique was used to prepare VG microparticles. Compritol® was heated at 10 oC above its melting point and VG was dispersed in the molten carrier using a homogenizer (IKA T25- USA) set at 13000 rpm. VG dispersed in the molten Compritol® was added dropwise to the molten Gelucire® 50/13 and PEG® (400, 6000, and 35000) in different ratios under manual stirring. The molten mixture was homogenized and Carbomer® amount was added. The melt was pumped through the two-fluid nozzle of the Buchi® Spray-Congealer (Buchi B-290, Switzerland) using a Pump drive (Master flex, USA) connected to a silicone tubing wrapped with silicone heating tape heated at the same temperature of the pumped mix. The physicochemical properties of the produced VG-loaded microparticles were characterized using Mastersizer, Scanning Electron Microscope (SEM), Differential Scanning Calorimeter (DSC) and X‐Ray Diffractometer (XRD). VG microparticles were then pressed into tablets using a single punch tablet machine (YDP-12, Minhua pharmaceutical Co. China) and in vitro dissolution study was investigated using Agilent Dissolution Tester (Agilent, USA). The dissolution test was carried out at 37±0.5 °C for 24 hours in three different dissolution media and time phases. The quantitative analysis of VG in samples was realized using a validated High-Pressure Liquid Chromatography (HPLC-UV) method. Results: The microparticles were spherical in shape with narrow distribution and smooth surface. DSC and XRD analyses confirmed the crystallinity of VG that was lost after being incorporated into the amorphous polymers. The total yields of the different formulas were between 70% and 80%. The VG content in the microparticles was found to be between 99% and 106%. The in vitro dissolution study showed that VG was released from the tableted particles in a controlled fashion. The adjustment of the hydrophilic/hydrophobic ratio of excipients, their concentration and the molecular weight of the used carriers resulted in tablets with zero-order kinetics. The Gelucire 50/13®, a hydrophilic polymer was characterized by a time-dependent profile with an important burst effect that was decreased by adding Compritol® as a lipophilic carrier to retard the release of VG which is highly soluble in water. PEG® (400,6000 and 35 000) were used for their gelling effect that led to a constant rate delivery and achieving a zero-order profile. Conclusion: Tableted spray-congealed lipid microparticles for extended-release of VG were successfully prepared and a zero-order profile was achieved.

Keywords: vildagliptin, spray congealing, microparticles, controlled release

Procedia PDF Downloads 106
71 Optical and Structural Characterization of Rare Earth Doped Phosphate Glasses

Authors: Zélia Maria Da Costa Ludwig, Maria José Valenzuela Bell, Geraldo Henriques Da Silva, Thales Alves Faraco, Victor Rocha Da Silva, Daniel Rotmeister Teixeira, Vírgilio De Carvalho Dos Anjos, Valdemir Ludwig

Abstract:

Advances in telecommunications grow with the development of optical amplifiers based on rare earth ions. The focus has been concentrated in silicate glasses although their amplified spontaneous emission is limited to a few tens of nanometers (~ 40nm). Recently, phosphate glasses have received great attention due to their potential application in optical data transmission, detection, sensors and laser detector, waveguide and optical fibers, besides its excellent physical properties such as high thermal expansion coefficients and low melting temperature. Compared with the silica glasses, phosphate glasses provide different optical properties such as, large transmission window of infrared, and good density. Research on the improvement of physical and chemical durability of phosphate glass by addition of heavy metals oxides in P2O5 has been performed. The addition of Na2O further improves the solubility of rare earths, while increasing the Al2O3 links in the P2O5 tetrahedral results in increased durability and aqueous transition temperature and a decrease of the coefficient of thermal expansion. This work describes the structural and spectroscopic characterization of a phosphate glass matrix doped with different Er (Erbium) concentrations. The phosphate glasses containing Er3+ ions have been prepared by melt technique. A study of the optical absorption, luminescence and lifetime was conducted in order to characterize the infrared emission of Er3+ ions at 1540 nm, due to the radiative transition 4I13/2 → 4I15/2. Our results indicate that the present glass is a quite good matrix for Er3+ ions, and the quantum efficiency of the 1540 nm emission was high. A quenching mechanism for the mentioned luminescence was not observed up to 2,0 mol% of Er concentration. The Judd-Ofelt parameters, radiative lifetime and quantum efficiency have been determined in order to evaluate the potential of Er3+ ions in new phosphate glass. The parameters follow the trend as Ω2 > Ω4 > Ω6. It is well known that the parameter Ω2 is an indication of the dominant covalent nature and/or structural changes in the vicinity of the ion (short range effects), while Ω4 and Ω6 intensity parameters are long range parameters that can be related to the bulk properties such as viscosity and rigidity of the glass. From the PL measurements, no red or green upconversion was measured when pumping the samples with laser excitation at 980 nm. As future prospects: Synthesize this glass system with silver in order to determine the influence of silver nanoparticles on the Er3+ ions.

Keywords: phosphate glass, erbium, luminescence, glass system

Procedia PDF Downloads 489
70 Catalytic Ammonia Decomposition: Cobalt-Molybdenum Molar Ratio Effect on Hydrogen Production

Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez

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Catalytic ammonia decomposition represents an attractive alternative due to its high H₂ content (17.8% w/w), a product stream free of COₓ, among others; however, challenges need to be addressed for its consolidation as an H₂ chemical storage technology, especially, those focused on the synthesis of efficient bimetallic catalytic systems, as an alternative to the price and scarcity of ruthenium, the most active catalyst reported. In this sense, from the perspective of rational catalyst design, adjusting the main catalytic activity descriptor, a screening of supported catalysts with different compositional settings of cobalt-molybdenum metals is presented to evaluate their effect on the catalytic decomposition rate of ammonia. Subsequently, a kinetic study on the supported monometallic Co and Mo catalysts, as well as on the bimetallic CoMo catalyst with the highest activity is shown. The synthesis of catalysts supported on γ-alumina was carried out using the Charge Enhanced Dry Impregnation (CEDI) method, all with a 5% w/w loading metal. Seeking to maintain uniform dispersion, the catalysts were oxidized and activated (In-situ activation) using a flow of anhydrous air and hydrogen, respectively, under the same conditions: 40 ml min⁻¹ and 5 °C min⁻¹ from room temperature to 600 °C. Catalytic tests were carried out in a fixed-bed reactor, confirming the absence of transport limitations, as well as an Approach to equilibrium (< 1 x 10⁻⁴). The reaction rate on all catalysts was measured between 400 and 500 ºC at 53.09 kPa NH3. The synergy theoretically (DFT) reported for bimetallic catalysts was confirmed experimentally. Specifically, it was observed that the catalyst composed mainly of 75 mol% cobalt proved to be the most active in the experiments, followed by the monometallic cobalt and molybdenum catalysts, in this order of activity as referred to in the literature. A kinetic study was performed at 10.13 – 101.32 kPa NH3 and at four equidistant temperatures between 437 and 475 °C the data were adjusted to an LHHW-type model, which considered the desorption of nitrogen atoms from the active phase surface as the rate determining step (RDS). The regression analysis were carried out under an integral regime, using a minimization algorithm based on SLSQP. The physical meaning of the parameters adjusted in the kinetic model, such as the RDS rate constant (k₅) and the lumped adsorption constant of the quasi-equilibrated steps (α) was confirmed through their Arrhenius and Van't Hoff-type behavior (R² > 0.98), respectively. From an energetic perspective, the activation energy for cobalt, cobalt-molybdenum, and molybdenum was 115.2, 106.8, and 177.5 kJ mol⁻¹, respectively. With this evidence and considering the volcano shape described by the ammonia decomposition rate in relation to the metal composition ratio, the synergistic behavior of the system is clearly observed. However, since characterizations by XRD and TEM were inconclusive, the formation of intermetallic compounds should be still verified using HRTEM-EDS. From this point onwards, our objective is to incorporate parameters into the kinetic expressions that consider both compositional and structural elements and explore how these can maximize or influence H₂ production.

Keywords: CEDI, hydrogen carrier, LHHW, RDS

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69 Improvement of the Traditional Techniques of Artistic Casting through the Development of Open Source 3D Printing Technologies Based on Digital Ultraviolet Light Processing

Authors: Drago Diaz Aleman, Jose Luis Saorin Perez, Cecile Meier, Itahisa Perez Conesa, Jorge De La Torre Cantero

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Traditional manufacturing techniques used in artistic contexts compete with highly productive and efficient industrial procedures. The craft techniques and associated business models tend to disappear under the pressure of the appearance of mass-produced products that compete in all niche markets, including those traditionally reserved for the work of art. The surplus value derived from the prestige of the author, the exclusivity of the product or the mastery of the artist, do not seem to be sufficient reasons to preserve this productive model. In the last years, the adoption of open source digital manufacturing technologies in small art workshops can favor their permanence by assuming great advantages such as easy accessibility, low cost, and free modification, adapting to specific needs of each workshop. It is possible to use pieces modeled by computer and made with FDM (Fused Deposition Modeling) 3D printers that use PLA (polylactic acid) in the procedures of artistic casting. Models printed by PLA are limited to approximate minimum sizes of 3 cm, and optimal layer height resolution is 0.1 mm. Due to these limitations, it is not the most suitable technology for artistic casting processes of smaller pieces. An alternative to solve size limitation, are printers from the type (SLS) "selective sintering by laser". And other possibility is a laser hardens, by layers, metal powder and called DMLS (Direct Metal Laser Sintering). However, due to its high cost, it is a technology that is difficult to introduce in small artistic foundries. The low-cost DLP (Digital Light Processing) type printers can offer high resolutions for a reasonable cost (around 0.02 mm on the Z axis and 0.04 mm on the X and Y axes), and can print models with castable resins that allow the subsequent direct artistic casting in precious metals or their adaptation to processes such as electroforming. In this work, the design of a DLP 3D printer is detailed, using backlit LCD screens with ultraviolet light. Its development is totally "open source" and is proposed as a kit made up of electronic components, based on Arduino and easy to access mechanical components in the market. The CAD files of its components can be manufactured in low-cost FDM 3D printers. The result is less than 500 Euros, high resolution and open-design with free access that allows not only its manufacture but also its improvement. In future works, we intend to carry out different comparative analyzes, which allow us to accurately estimate the print quality, as well as the real cost of the artistic works made with it.

Keywords: traditional artistic techniques, DLP 3D printer, artistic casting, electroforming

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68 Effect of Ti, Nb, and Zr Additives on Biocompatibility of Injection Molded 316L Stainless Steel for Biomedical Applications

Authors: Busra Gundede, Ozal Mutlu, Nagihan Gulsoy

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Background: Over the years, material research has led to the development of numerous metals and alloys for using in biomedical applications. One of the major tasks of biomaterial research is the functionalization of the material surface to improve the biocompatibility according to a specific application. 316L and 316L alloys are excellent for various bio-applications. This research was investigated the effect of titanium (Ti), niobium (Nb), and zirconium (Zr) additives on injection molded austenitic grade 316L stainless steels in vitro biocompatibility. For this purpose, cytotoxic tests were performed to evaluate the potential biocompatibility of the specimens. Materials and Methods: 3T3 fibroblast were cultivated in DMEM supplemented with 10% fetal bovine serum and %1 penicillin-streptomycin at 37°C with 5% CO2 and 95%humidity. Trypsin/EDTA solution was used to remove cells from the culture flask. Cells were reseeded at a density of 1×105cell in 25T flasks. The medium change took place every 3 days. The trypan blue assay was used to determine cell viability. Cell viability is calculated as the number of viable cells divided by the total number of cells within the grids on the cell counter machine counted the number of blue staining cells and the number of total cells. Cell viability should be at least 95% for healthy log-phase cultures. MTT assay was assessed for 96-hours. Cells were cultivated in 6-well flask within 5 ml DMEM and incubated as same conditions. 0,5mg/ml MTT was added for 4-hours and then acid-isoprohanol was added for solubilize to formazan crystals. Cell morphology after 96h was investigated by SEM. The medium was removed, samples were washed with 0.15 M PBS buffer and fixed for 12h at 4- 8°C with %2,5 gluteraldehyte. Samples were treated with 1% osmium tetroxide. Samples were then dehydrated and dried, mounted on appropriate stubs with colloidal silver and sputter-coated with gold. Images were collected using a scanning electron microscope. ROS assay is a cell viability test for in vitro studies. Cells were grown for 96h, ROS solution added on cells in 6 well plate flask and incubated for 1h. Fluorescence signal indicates ROS generation by cells. Results: Trypan Blue exclusion assay results were 96%, 92%, 95%, 90%, 91% for negative control group, 316L, 316L-Ti, 316L-Nb and 316L-Zr, respectively. Results were found nearly similar to each other when compared with control group. Cell viability from MTT analysis was found to be 100%, 108%, 103%, 107%, and 105% for the control group, 316L, 316L-Ti, 316L-Nb and 316L-Zr, respectively. Fluorescence microscopy analysis indicated that all test groups were same as the control group in ROS assay. SEM images demonstrated that the attachment of 3T3 cells on biomaterials. Conclusion: We, therefore, concluded that Ti, Nb and Zr additives improved physical properties of 316L stainless. In our in vitro experiments showed that these new additives did not modify the cytocompatibility of stainless steel and these additives on 316L might be useful for biomedical applications.

Keywords: 316L stainles steel, biocompatibility, cell culture, Ti, Nb, Zr

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67 Recycling the Lanthanides from Permanent Magnets by Electrochemistry in Ionic Liquid

Authors: Celine Bonnaud, Isabelle Billard, Nicolas Papaiconomou, Eric Chainet

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Thanks to their high magnetization and low mass, permanent magnets (NdFeB and SmCo) have quickly became essential for new energies (wind turbines, electrical vehicles…). They contain large quantities of neodymium, samarium and dysprosium, that have been recently classified as critical elements and that therefore need to be recycled. Electrochemical processes including electrodissolution followed by electrodeposition are an elegant and environmentally friendly solution for the recycling of such lanthanides contained in permanent magnets. However, electrochemistry of the lanthanides is a real challenge as their standard potentials are highly negative (around -2.5V vs ENH). Consequently, non-aqueous solvents are required. Ionic liquids (IL) are novel electrolytes exhibiting physico-chemical properties that fulfill many requirements of the sustainable chemistry principles, such as extremely low volatility and non-flammability. Furthermore, their chemical and electrochemical properties (solvation of metallic ions, large electrochemical windows, etc.) render them very attractive media to implement alternative and sustainable processes in view of integrated processes. All experiments that will be presented were carried out using butyl-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide. Linear sweep, cyclic voltammetry and potentiostatic electrochemical techniques were used. The reliability of electrochemical experiments, performed without glove box, for the classic three electrodes cell used in this study has been assessed. Deposits were obtained by chronoamperometry and were characterized by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The IL cathodic behavior under different constraints (argon, nitrogen, oxygen atmosphere or water content) and using several electrode materials (Pt, Au, GC) shows that with argon gas flow and gold as a working electrode, the cathodic potential can reach the maximum value of -3V vs Fc+/Fc; thus allowing a possible reduction of lanthanides. On a gold working electrode, the reduction potential of samarium and neodymium was found to be -1.8V vs Fc+/Fc while that of dysprosium was -2.1V vs Fc+/Fc. The individual deposits obtained were found to be porous and presented some significant amounts of C, N, F, S and O atoms. Selective deposition of neodymium in presence of dysprosium was also studied and will be discussed. Next, metallic Sm, Nd and Dy electrodes were used in replacement of Au, which induced changes in the reduction potential values and the deposit structures of lanthanides. The individual corrosion potentials were also measured in order to determine the parameters influencing the electrodissolution of these metals. Finally, a full recycling process was investigated. Electrodissolution of a real permanent magnet sample was monitored kinetically. Then, the sequential electrodeposition of all lanthanides contained in the IL was investigated. Yields, quality of the deposits and consumption of chemicals will be discussed in depth, in view of the industrial feasibility of this process for real permanent magnets recycling.

Keywords: electrodeposition, electrodissolution, ionic liquids, lanthanides, rcycling

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66 HyDUS Project; Seeking a Wonder Material for Hydrogen Storage

Authors: Monica Jong, Antonios Banos, Tom Scott, Chris Webster, David Fletcher

Abstract:

Hydrogen, as a clean alternative to methane, is relatively easy to make, either from water using electrolysis or from methane using steam reformation. However, hydrogen is much trickier to store than methane, and without effective storage, it simply won’t pass muster as a suitable methane substitute. Physical storage of hydrogen is quite inefficient. Storing hydrogen as a compressed gas at pressures up to 900 times atmospheric is volumetrically inefficient and carries safety implications, whilst storing it as a liquid requires costly and constant cryogenic cooling to minus 253°C. This is where DU steps in as a possible solution. Across the periodic table, there are many different metallic elements that will react with hydrogen to form a chemical compound known as a hydride (or metal hydride). From a chemical perspective, the ‘king’ of the hydride forming metals is palladium because it offers the highest hydrogen storage volumetric capacity. However, this material is simply too expensive and scarce to be used in a scaled-up bulk hydrogen storage solution. Depleted Uranium is the second most volumetrically efficient hydride-forming metal after palladium. The UK has accrued a significant amount of DU because of manufacturing nuclear fuel for many decades, and that is currently without real commercial use. Uranium trihydride (UH3) contains three hydrogen atoms for every uranium atom and can chemically store hydrogen at ambient pressure and temperature at more than twice the density of pure liquid hydrogen for the same volume. To release the hydrogen from the hydride, all you do is heat it up. At temperatures above 250°C, the hydride starts to thermally decompose, releasing hydrogen as a gas and leaving the Uranium as a metal again. The reversible nature of this reaction allows the hydride to be formed and unformed again and again, enabling its use as a high-density hydrogen storage material which is already available in large quantities because of its stockpiling as a ‘waste’ by-product. Whilst the tritium storage credentials of Uranium have been rigorously proven at the laboratory scale and at the fusion demonstrator JET for over 30 years, there is a need to prove the concept for depleted uranium hydrogen storage (HyDUS) at scales towards that which is needed to flexibly supply our national power grid with energy. This is exactly the purpose of the HyDUS project, a collaborative venture involving EDF as the interested energy vendor, Urenco as the owner of the waste DU, and the University of Bristol with the UKAEA as the architects of the technology. The team will embark on building and proving the world’s first pilot scale demonstrator of bulk chemical hydrogen storage using depleted Uranium. Within 24 months, the team will attempt to prove both the technical and commercial viability of this technology as a longer duration energy storage solution for the UK. The HyDUS project seeks to enable a true by-product to wonder material story for depleted Uranium, demonstrating that we can think sustainably about unlocking the potential value trapped inside nuclear waste materials.

Keywords: hydrogen, long duration storage, storage, depleted uranium, HyDUS

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65 Standardization of the Roots of Gnidia stenophylla Gilg: A Potential Medicinal Plant of South Eastern Ethiopia Traditionally Used as an Antimalarial

Authors: Mebruka Mohammed, Daniel Bisrat, Asfaw Debella, Tarekegn Birhanu

Abstract:

Lack of quality control standards for medicinal plants and their preparations is considered major barrier to their integration in to effective primary health care in Ethiopia. Poor quality herbal preparations led to countless adverse reactions extending to death. Denial of penetration for the Ethiopian medicinal plants in to the world’s booming herbal market is also another significant loss resulting from absence of herbal quality control system. Thus, in the present study, Gnidia stenophylla Gilg (popular antimalarial plant of south eastern Ethiopia), is standardized and a full monograph is produced that can serve as a guideline in quality control of the crude drug. Morphologically, the roots are found to be cylindrical and tapering towards the end. It has a hard, corky and friable touch with saddle brown color externally and it is relatively smooth and pale brown internally. It has got characteristic pungent odor and very bitter taste. Microscopically it has showed lignified xylem vessels, wider medullary rays with some calcium oxalate crystals, reddish brown secondary metabolite contents and slender shaped long fibres. Physicochemical standards quantified and resulted: foreign matter (5.25%), moisture content (6.69%), total ash (40.80%), acid insoluble ash (8.00%), water soluble ash (2.30%), alcohol soluble extractive (15.27%), water soluble extractive (10.98%), foaming index (100.01 ml/g), swelling index (7.60 ml/g). Phytochemically: Phenols, flavonoids, steroids, tannins and saponins were detected in the root extract; TLC and HPLC fingerprints were produced and an analytical marker was also tentatively characterized as 3-(3,4-dihydro-3,5-dihydroxy-2-(4-hydroxy-5-methylhex-1-en-2-yl)-7-methoxy-4-oxo-2H-chromen-8-yl)-5-hydroxy-2-(4-hydroxyphenyl)-7-methoxy-4H-chromen-4-one. Residue wise pesticides (i.e. DDT, DDE, g-BHC) and radiochemical levels fall below the WHO limit while Heavy metals (i.e. Co, Ni, Cr, Pb, and Cu), total aerobic count and fungal load lie way above the WHO limit. In conclusion, the result can be taken as signal that employing non standardized medicinal plants could cause many health risks of the Ethiopian people and Africans’ at large (as 80% of inhabitants in the continent depends on it for primary health care). Therefore, following a more universal approach to herbal quality by adopting the WHO guidelines and developing monographs using the various quality parameters is inevitable to minimize quality breach and promote effective herbal drug usage.

Keywords: Gnidia stenophylla Gilg, standardization/monograph, pharmacognostic, residue/impurity, quality

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64 Ectopic Osteoinduction of Porous Composite Scaffolds Reinforced with Graphene Oxide and Hydroxyapatite Gradient Density

Authors: G. M. Vlasceanu, H. Iovu, E. Vasile, M. Ionita

Abstract:

Herein, the synthesis and characterization of chitosan-gelatin highly porous scaffold reinforced with graphene oxide, and hydroxyapatite (HAp), crosslinked with genipin was targeted. In tissue engineering, chitosan and gelatin are two of the most robust biopolymers with wide applicability due to intrinsic biocompatibility, biodegradability, low antigenicity properties, affordability, and ease of processing. HAp, per its exceptional activity in tuning cell-matrix interactions, is acknowledged for its capability of sustaining cellular proliferation by promoting bone-like native micro-media for cell adjustment. Genipin is regarded as a top class cross-linker, while graphene oxide (GO) is viewed as one of the most performant and versatile fillers. The composites with natural bone HAp/biopolymer ratio were obtained by cascading sonochemical treatments, followed by uncomplicated casting methods and by freeze-drying. Their structure was characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction, while overall morphology was investigated by Scanning Electron Microscopy (SEM) and micro-Computer Tomography (µ-CT). Ensuing that, in vitro enzyme degradation was performed to detect the most promising compositions for the development of in vivo assays. Suitable GO dispersion was ascertained within the biopolymer mix as nanolayers specific signals lack in both FTIR and XRD spectra, and the specific spectral features of the polymers persisted with GO load enhancement. Overall, correlations between the GO induced material structuration, crystallinity variations, and chemical interaction of the compounds can be correlated with the physical features and bioactivity of each composite formulation. Moreover, the HAp distribution within follows an auspicious density gradient tuned for hybrid osseous/cartilage matter architectures, which were mirrored in the mice model tests. Hence, the synthesis route of a natural polymer blend/hydroxyapatite-graphene oxide composite material is anticipated to emerge as influential formulation in bone tissue engineering. Acknowledgement: This work was supported by the project 'Work-based learning systems using entrepreneurship grants for doctoral and post-doctoral students' (Sisteme de invatare bazate pe munca prin burse antreprenor pentru doctoranzi si postdoctoranzi) - SIMBA, SMIS code 124705 and by a grant of the National Authority for Scientific Research and Innovation, Operational Program Competitiveness Axis 1 - Section E, Program co-financed from European Regional Development Fund 'Investments for your future' under the project number 154/25.11.2016, P_37_221/2015. The nano-CT experiments were possible due to European Regional Development Fund through Competitiveness Operational Program 2014-2020, Priority axis 1, ID P_36_611, MySMIS code 107066, INOVABIOMED.

Keywords: biopolymer blend, ectopic osteoinduction, graphene oxide composite, hydroxyapatite

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63 Environmental Catalysts for Refining Technology Application: Reduction of CO Emission and Gasoline Sulphur in Fluid Catalytic Cracking Unit

Authors: Loganathan Kumaresan, Velusamy Chidambaram, Arumugam Velayutham Karthikeyani, Alex Cheru Pulikottil, Madhusudan Sau, Gurpreet Singh Kapur, Sankara Sri Venkata Ramakumar

Abstract:

Environmentally driven regulations throughout the world stipulate dramatic improvements in the quality of transportation fuels and refining operations. The exhaust gases like CO, NOx, and SOx from stationary sources (e.g., refinery) and motor vehicles contribute to a large extent for air pollution. The refining industry is under constant environmental pressure to achieve more rigorous standards on sulphur content in the fuel used in the transportation sector and other off-gas emissions. Fluid catalytic cracking unit (FCCU) is a major secondary process in refinery for gasoline and diesel production. CO-combustion promoter additive and gasoline sulphur reduction (GSR) additive are catalytic systems used in FCCU to assist the combustion of CO to CO₂ in the regenerator and regulate sulphur in gasoline faction respectively along with main FCC catalyst. Effectiveness of these catalysts is governed by the active metal used, its dispersion, the type of base material employed, and retention characteristics of additive in FCCU such as attrition resistance and density. The challenge is to have a high-density microsphere catalyst support for its retention and high activity of the active metals as these catalyst additives are used in low concentration compare to the main FCC catalyst. The present paper discusses in the first part development of high dense microsphere of nanocrystalline alumina by hydro-thermal method for CO combustion promoter application. Performance evaluation of additive was conducted under simulated regenerator conditions and shows CO combustion efficiency above 90%. The second part discusses the efficacy of a co-precipitation method for the generation of the active crystalline spinels of Zn, Mg, and Cu with aluminium oxides as an additive. The characterization and micro activity test using heavy combined hydrocarbon feedstock at FCC unit conditions for evaluating gasoline sulphur reduction activity are studied. These additives were characterized by X-Ray Diffraction, NH₃-TPD & N₂ sorption analysis, TPR analysis to establish structure-activity relationship. The reaction of sulphur removal mechanisms involving hydrogen transfer reaction, aromatization and alkylation functionalities are established to rank GSR additives for their activity, selectivity, and gasoline sulphur removal efficiency. The sulphur shifting in other liquid products such as heavy naphtha, light cycle oil, and clarified oil were also studied. PIONA analysis of liquid product reveals 20-40% reduction of sulphur in gasoline without compromising research octane number (RON) of gasoline and olefins content.

Keywords: hydrothermal, nanocrystalline, spinel, sulphur reduction

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62 Insights into Particle Dispersion, Agglomeration and Deposition in Turbulent Channel Flow

Authors: Mohammad Afkhami, Ali Hassanpour, Michael Fairweather

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The work described in this paper was undertaken to gain insight into fundamental aspects of turbulent gas-particle flows with relevance to processes employed in a wide range of applications, such as oil and gas flow assurance in pipes, powder dispersion from dry powder inhalers, and particle resuspension in nuclear waste ponds, to name but a few. In particular, the influence of particle interaction and fluid phase behavior in turbulent flow on particle dispersion in a horizontal channel is investigated. The mathematical modeling technique used is based on the large eddy simulation (LES) methodology embodied in the commercial CFD code FLUENT, with flow solutions provided by this approach coupled to a second commercial code, EDEM, based on the discrete element method (DEM) which is used for the prediction of particle motion and interaction. The results generated by LES for the fluid phase have been validated against direct numerical simulations (DNS) for three different channel flows with shear Reynolds numbers, Reτ = 150, 300 and 590. Overall, the LES shows good agreement, with mean velocities and normal and shear stresses matching those of the DNS in both magnitude and position. The research work has focused on the prediction of those conditions favoring particle aggregation and deposition within turbulent flows. Simulations have been carried out to investigate the effects of particle size, density and concentration on particle agglomeration. Furthermore, particles with different surface properties have been simulated in three channel flows with different levels of flow turbulence, achieved by increasing the Reynolds number of the flow. The simulations mimic the conditions of two-phase, fluid-solid flows frequently encountered in domestic, commercial and industrial applications, for example, air conditioning and refrigeration units, heat exchangers, oil and gas suction and pressure lines. The particle size, density, surface energy and volume fractions selected are 45.6, 102 and 150 µm, 250, 1000 and 2159 kg m-3, 50, 500, and 5000 mJ m-2 and 7.84 × 10-6, 2.8 × 10-5, and 1 × 10-4, respectively; such particle properties are associated with particles found in soil, as well as metals and oxides prevalent in turbulent bounded fluid-solid flows due to erosion and corrosion of inner pipe walls. It has been found that the turbulence structure of the flow dominates the motion of the particles, creating particle-particle interactions, with most of these interactions taking place at locations close to the channel walls and in regions of high turbulence where their agglomeration is aided both by the high levels of turbulence and the high concentration of particles. A positive relationship between particle surface energy, concentration, size and density, and agglomeration was observed. Moreover, the results derived for the three Reynolds numbers considered show that the rate of agglomeration is strongly influenced for high surface energy particles by, and increases with, the intensity of the flow turbulence. In contrast, for lower surface energy particles, the rate of agglomeration diminishes with an increase in flow turbulence intensity.

Keywords: agglomeration, channel flow, DEM, LES, turbulence

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61 Molecular Migration in Polyvinyl Acetate Matrix: Impact of Compatibility, Number of Migrants and Stress on Surface and Internal Microstructure

Authors: O. Squillace, R. L. Thompson

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Migration of small molecules to, and across the surface of polymer matrices is a little-studied problem with important industrial applications. Tackifiers in adhesives, flavors in foods and binding agents in paints all present situations where the function of a product depends on the ability of small molecules to migrate through a polymer matrix to achieve the desired properties such as softness, dispersion of fillers, and to deliver an effect that is felt (or tasted) on a surface. It’s been shown that the chemical and molecular structure, surface free energies, phase behavior, close environment and compatibility of the system, influence the migrants’ motion. When differences in behavior, such as occurrence of segregation to the surface or not, are observed it is then of crucial importance to identify and get a better understanding of the driving forces involved in the process of molecular migration. In this aim, experience is meant to be allied with theory in order to deliver a validated theoretical and computational toolkit to describe and predict these phenomena. The systems that have been chosen for this study aim to address the effect of polarity mismatch between the migrants and the polymer matrix and that of a second migrant over the first one. As a non-polar resin polymer, polyvinyl acetate is used as the material to which more or less polar migrants (sorbitol, carvone, octanoic acid (OA), triacetin) are to be added. Through contact angle measurement a surface excess is seen for sorbitol (polar) mixed with PVAc as the surface energy is lowered compare to the one of pure PVAc. This effect is increased upon the addition of carvon or triacetin (non-polars). Surface micro-structures are also evidenced by atomic force microscopy (AFM). Ion beam analysis (Nuclear Reaction Analysis), supplemented by neutron reflectometry can accurately characterize the self-organization of surfactants, oligomers, aromatic molecules in polymer films in order to relate the macroscopic behavior to the length scales that are amenable to simulation. The nuclear reaction analysis (NRA) data for deuterated OA 20% shows the evidence of a surface excess which is enhanced after annealing. The addition of 10% triacetin, as a second migrant, results in the formation of an underlying layer enriched in triacetin below the surface excess of OA. The results show that molecules in polarity mismatch with the matrix tend to segregate to the surface, and this is favored by the addition of a second migrant of the same polarity than the matrix. As studies have been restricted to materials that are model supported films under static conditions in a first step, it is also wished to address the more challenging conditions of materials under controlled stress or strain. To achieve this, a simple rig and PDMS cell have been designed to stretch the material to a defined strain and to probe these mechanical effects by ion beam analysis and atomic force microscopy. This will make a significant step towards exploring the influence of extensional strain on surface segregation, flavor release in cross-linked rubbers.

Keywords: polymers, surface segregation, thin films, molecular migration

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60 Investigation of Physical Properties of Asphalt Binder Modified by Recycled Polyethylene and Ground Tire Rubber

Authors: Sajjad H. Kasanagh, Perviz Ahmedzade, Alexander Fainleib, Taylan Gunay

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Modification of asphalt is a fundamental method around the world mainly on the purpose of providing more durable pavements which lead to diminish repairing cost during the lifetime of highways. Various polymers such as styrene-butadiene-styrene (SBS) and ethylene vinyl acetate (EVA) make up the greater parts of the all-over asphalt modifiers generally providing better physical properties of asphalt by decreasing temperature dependency which eventually diminishes permanent deformation on highways such as rutting. However, some waste and low-cost materials such as recycled plastics and ground rubber tire have been attempted to utilize in asphalt as modifier instead of manufactured polymer modifiers due to decreasing the eventual highway cost. On the other hand, the usage of recycled plastics has become a worldwide requirement and awareness in order to decrease the pollution made by waste plastics. Hence, finding an area in which recycling plastics could be utilized has been targeted by many research teams so as to reduce polymer manufacturing and plastic pollution. To this end, in this paper, thermoplastic dynamic vulcanizate (TDV) obtained from recycled post-consumer polyethylene and ground tire rubber (GTR) were used to provide an efficient modifier for asphalt which decreases the production cost as well and finally might provide an ecological solution by decreasing polymer disposal problems. TDV was synthesized by the chemists in the research group by means of the abovementioned components that are considered as compatible physical characteristic of asphalt materials. TDV modified asphalt samples having different rate of proportions of 3, 4, 5, 6, 7 wt.% TDV modifier were prepared. Conventional tests, such as penetration, softening point and roll thin film oven (RTFO) tests were performed to obtain fundamental physical and aging properties of the base and modified binders. The high temperature performance grade (PG) of binders was determined by Superpave tests conducted on original and aged binders. The multiple stress creep and recovery (MSCR) test which is relatively up-to-date method for classifying asphalts taking account of their elasticity abilities was carried out to evaluate PG plus grades of binders. The results obtained from performance grading, and MSCR tests were also evaluated together so as to make a comparison between the methods both aiming to determine rheological parameters of asphalt. The test results revealed that TDV modification leads to a decrease in penetration, an increase in softening point, which proves an increasing stiffness of asphalt. DSR results indicate an improvement in PG for modified binders compared to base asphalt. On the other hand, MSCR results that are compatible with DSR results also indicate an enhancement on rheological properties of asphalt. However, according to the results, the improvement is not as distinct as observed in DSR results since elastic properties are fundamental in MSCR. At the end of the testing program, it can be concluded that TDV can be used as modifier which provides better rheological properties for asphalt and might diminish plastic waste pollution since the material is 100% recycled.

Keywords: asphalt, ground tire rubber, recycled polymer, thermoplastic dynamic vulcanizate

Procedia PDF Downloads 197