Search results for: on-orbit manufacture
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 437

Search results for: on-orbit manufacture

47 Influence of Intra-Yarn Permeability on Mesoscale Permeability of Plain Weave and 3D Fabrics

Authors: Debabrata Adhikari, Mikhail Matveev, Louise Brown, Andy Long, Jan Kočí

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A good understanding of mesoscale permeability of complex architectures in fibrous porous preforms is of particular interest in order to achieve efficient and cost-effective resin impregnation of liquid composite molding (LCM). Fabrics used in structural reinforcements are typically woven or stitched. However, 3D fabric reinforcement is of particular interest because of the versatility in the weaving pattern with the binder yarn and in-plain yarn arrangements to manufacture thick composite parts, overcome the limitation in delamination, improve toughness etc. To predict the permeability based on the available pore spaces between the inter yarn spaces, unit cell-based computational fluid dynamics models have been using the Stokes Darcy model. Typically, the preform consists of an arrangement of yarns with spacing in the order of mm, wherein each yarn consists of thousands of filaments with spacing in the order of μm. The fluid flow during infusion exchanges the mass between the intra and inter yarn channels, meaning there is no dead-end of flow between the mesopore in the inter yarn space and the micropore in the yarn. Several studies have employed the Brinkman equation to take into account the flow through dual-scale porosity reinforcement to estimate their permeability. Furthermore, to reduce the computational effort of dual scale flow, scale separation criteria based on the ratio between yarn permeability to the yarn spacing was also proposed to quantify the dual scale and negligible micro-scale flow regime for the prediction of mesoscale permeability. In the present work, the key parameter to identify the influence of intra yarn permeability on the mesoscale permeability has been investigated with the systematic study of weft and warp yarn spacing on the plane weave as well as the position of binder yarn and number of in-plane yarn layers on 3D weave fabric. The permeability tensor has been estimated using an OpenFOAM-based model for the various weave pattern with idealized geometry of yarn implemented using open-source software TexGen. Additionally, scale separation criterion has been established based on the various configuration of yarn permeability for the 3D fabric with both the isotropic and anisotropic yarn from Gebart’s model. It was observed that the variation of mesoscale permeability Kxx within 30% when the isotropic porous yarn is considered for a 3D fabric with binder yarn. Furthermore, the permeability model developed in this study will be used for multi-objective optimizations of the preform mesoscale geometry in terms of yarn spacing, binder pattern, and a number of layers with an aim to obtain improved permeability and reduced void content during the LCM process.

Keywords: permeability, 3D fabric, dual-scale flow, liquid composite molding

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46 Physico-Chemical and Biotechnological Characterization of Sheep’s Milk (Ovis aries) by Three Medicinal Plants Extracts

Authors: Fatima Bouazza, Khadija Khedid, Lamiae Amallah, Aziz Mouhaddach, Basma Boukour, Jihane Ennadir, Rachida Hassikou

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In order to combine milk and its derived products conservation and flavoring, Moroccans often used aromatic and medicinal plants. These plant extracts are endowed with several nutritive and therapeutic properties. This study constitutes a first national assessment of physico-chemical quality of sheep’s milk from moroccan Sardi breed and the evaluation of the antibacterial effect of three medicinal plants extracts: Aloe barbadensis Miller, Thymus satureioides and Mentha pulegium on flora isolated from this sheep's milk. 100 milk samples were collected in four regions of Morocco. The bacteria isolated were identified by classical and molecular methods (16S rRNA sequencing) and tested, according to the disk method, for their sensitivity to several antibiotics. The physico-chemical analyzes of sheep’s milk concerned the pH, titratable acidity, density, dry extract, freezing point and contents of: fat, proteins, lactose and calcium. The essential oils (EOs) of T. satureioides and M .pulegium were extracted by hydrodistillation and analyzed by GC / MS, while the Aloe vera leaf pulp was analyzed by the methods of Harborne and HPLC. A total number of 125 bacteria have been identified. Significant resistance to chemical antibiotics has been noted in LABs. The average temperature value of milk is around 57.15 °C, the pH is 6.56, the titratable acidity is around 3.4 ° D, the density is 1.035g / cm³ , the total dry extract is around 169.5g / l, the ash (9.8g / l), the freezing point (- 0.556 °C) while the average fat content is 67.85g / l . The samples richest in fat belong to the region of Settat, cradle of the Sardi breed, with a maximum average value of 74.4g / l. The average protein is 56g / l, lactose (39.92g / l), and calcium (1.855g / l). Analysis of the major components of EOs revealed the dominance of borneol in the case of T. satureioides and of pulegone in M. pulegium. Aloe vera gel contains alkaloids, flavonoids, catechic tannins, saponins and 1.60 µg / ml of aloin. The plant extracts have a bactericidal effect on E. coli, Klebsiellaoxytoca and Staphylococci and bacteriostatic effect on LABs of technological interest (Lactobacillus). As a result of this study, it is believed that the consumption of sardi sheep’s milk would be of nutritional benefit. Its richness in fat and proteins predisposes it for biotechnological development in the manufacture of cheese and yogurt. Also, the use of aromatic and medicinal plants, as natural additives would be of great benefit to flavor and maintain its quality.

Keywords: sheep’s milk, lactic flora, antimicrobial power, aloe barbadensis miller, thymus satureioides, mentha pulegium

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45 Isosorbide Bis-Methyl Carbonate: Opportunities for an Industrial Model Based on Biomass

Authors: Olga Gomez De Miranda, Jose R. Ochoa-Gomez, Stefaan De Wildeman, Luciano Monsegue, Soraya Prieto, Leire Lorenzo, Cristina Dineiro

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The chemical industry is facing a new revolution. As long as processes based on the exploitation of fossil resources emerged with force in the XIX century, Society currently demands a new radical change that will lead to the complete and irreversible implementation of a circular sustainable economic model. The implementation of biorefineries will be essential for this. There, renewable raw materials as sugars and other biomass resources are exploited for the development of new materials that will partially replace their petroleum-derived homologs in a safer, and environmentally more benign approach. Isosorbide, (1,4:3,6-dianhydro-d-glucidol) is a primary bio-based derivative obtained from the plant (poly) saccharides and a very interesting example of a useful chemical produced in biorefineries. It can, in turn, be converted to other secondary monomers as isosorbide bis-methyl carbonate (IBMC), whose main field of application can be as a key biodegradable intermediary substitute of bisphenol-A in the manufacture of polycarbonates, or as an alternative to the toxic isocyanates in the synthesis of new polyurethanes (non-isocyanate polyurethanes) both with a huge application market. New products will present advantageous mechanical or optical properties, as well as improved behavior in non-toxicity and biodegradability aspects in comparison to their petro-derived alternatives. A robust production process of IBMC, a biomass-derived chemical, is here presented. It can be used with different raw material qualities using dimethyl carbonate (DMC) as both co-reactant and solvent. It consists of the transesterification of isosorbide with DMC under soft operational conditions, using different basic catalysts, always active with the isosorbide characteristics and purity. Appropriate isolation processes have been also developed to obtain crude IBMC yields higher than 90%, with oligomers production lower than 10%, independently of the quality of the isosorbide considered. All of them are suitable to be used in polycondensation reactions for polymers obtaining. If higher qualities of IBMC are needed, a purification treatment based on nanofiltration membranes has been also developed. The IBMC reaction-isolation conditions established in the laboratory have been successfully modeled using appropriate software programs and moved to a pilot-scale (production of 100 kg of IBMC). It has been demonstrated that a highly efficient IBMC production process able to be up-scaled under suitable market conditions has been obtained. Operational conditions involved the production of IBMC involve soft temperature and energy needs, no additional solvents, and high operational efficiency. All of them are according to green manufacturing rules.

Keywords: biomass, catalyst, isosorbide bis-methyl carbonate, polycarbonate, polyurethane, transesterification

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44 Effect of Multi-Walled Carbon Nanotubes on Fuel Cell Membrane Performance

Authors: Rabindranath Jana, Biswajit Maity, Keka Rana

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The most promising clean energy source is the fuel cell, since it does not generate toxic gases and other hazardous compounds. Again the direct methanol fuel cell (DMFC) is more user-friendly as it is easy to be miniaturized and suited as energy source for automobiles as well as domestic applications and portable devices. And unlike the hydrogen used for some fuel cells, methanol is a liquid that is easy to store and transport in conventional tanks. The most important part of a fuel cell is its membrane. Till now, an overall efficiency for a methanol fuel cell is reported to be about 20 ~ 25%. The lower efficiency of the cell may be due to the critical factors, e.g. slow reaction kinetics at the anode and methanol crossover. The oxidation of methanol is composed of a series of successive reactions creating formaldehyde and formic acid as intermediates that contribute to slow reaction rates and decreased cell voltage. Currently, the investigation of new anode catalysts to improve oxidation reaction rates is an active area of research as it applies to the methanol fuel cell. Surprisingly, there are very limited reports on nanostructured membranes, which are rather simple to manufacture with different tuneable compositions and are expected to allow only the proton permeation but not the methanol due to their molecular sizing effects and affinity to the membrane surface. We have developed a nanostructured fuel cell membrane from polydimethyl siloxane rubber (PDMS), ethylene methyl co-acrylate (EMA) and multi-walled carbon nanotubes (MWNTs). The effect of incorporating different proportions of f-MWNTs in polymer membrane has been studied. The introduction of f-MWNTs in polymer matrix modified the polymer structure, and therefore the properties of the device. The proton conductivity, measured by an AC impedance technique using open-frame and two-electrode cell and methanol permeability of the membranes was found to be dependent on the f-MWNTs loading. The proton conductivity of the membranes increases with increase in concentration of f-MWNTs concentration due to increased content of conductive materials. Measured methanol permeabilities at 60oC were found to be dependant on loading of f-MWNTs. The methanol permeability decreased from 1.5 x 10-6 cm²/s for pure film to 0.8 x 10-7 cm²/s for a membrane containing 0.5wt % f-MWNTs. This is due to increasing proportion of f-MWNTs, the matrix becomes more compact. From DSC melting curves it is clear that the polymer matrix with f-MWNTs is thermally stable. FT-IR studies show good interaction between EMA and f-MWNTs. XRD analysis shows good crystalline behavior of the prepared membranes. Significant cost savings can be achieved when using the blended films which contain less expensive polymers.

Keywords: fuel cell membrane, polydimethyl siloxane rubber, carbon nanotubes, proton conductivity, methanol permeability

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43 Approach on Conceptual Design and Dimensional Synthesis of the Linear Delta Robot for Additive Manufacturing

Authors: Efrain Rodriguez, Cristhian Riano, Alberto Alvares

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In recent years, robots manipulators with parallel architectures are used in additive manufacturing processes – 3D printing. These robots have advantages such as speed and lightness that make them suitable to help with the efficiency and productivity of these processes. Consequently, the interest for the development of parallel robots for additive manufacturing applications has increased. This article deals with the conceptual design and dimensional synthesis of the linear delta robot for additive manufacturing. Firstly, a methodology based on structured processes for the development of products through the phases of informational design, conceptual design and detailed design is adopted: a) In the informational design phase the Mudge diagram and the QFD matrix are used to aid a set of technical requirements, to define the form, functions and features of the robot. b) In the conceptual design phase, the functional modeling of the system through of an IDEF0 diagram is performed, and the solution principles for the requirements are formulated using a morphological matrix. This phase includes the description of the mechanical, electro-electronic and computational subsystems that constitute the general architecture of the robot. c) In the detailed design phase, a digital model of the robot is drawn on CAD software. A list of commercial and manufactured parts is detailed. Tolerances and adjustments are defined for some parts of the robot structure. The necessary manufacturing processes and tools are also listed, including: milling, turning and 3D printing. Secondly, a dimensional synthesis method applied on design of the linear delta robot is presented. One of the most important key factors in the design of a parallel robot is the useful workspace, which strongly depends on the joint space, the dimensions of the mechanism bodies and the possible interferences between these bodies. The objective function is based on the verification of the kinematic model for a prescribed cylindrical workspace, considering geometric constraints that possibly lead to singularities of the mechanism. The aim is to determine the minimum dimensional parameters of the mechanism bodies for the proposed workspace. A method based on genetic algorithms was used to solve this problem. The method uses a cloud of points with the cylindrical shape of the workspace and checks the kinematic model for each of the points within the cloud. The evolution of the population (point cloud) provides the optimal parameters for the design of the delta robot. The development process of the linear delta robot with optimal dimensions for additive manufacture is presented. The dimensional synthesis enabled to design the mechanism of the delta robot in function of the prescribed workspace. Finally, the implementation of the robotic platform developed based on a linear delta robot in an additive manufacturing application using the Fused Deposition Modeling (FDM) technique is presented.

Keywords: additive manufacturing, delta parallel robot, dimensional synthesis, genetic algorithms

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42 Solutions to Reduce CO2 Emissions in Autonomous Robotics

Authors: Antoni Grau, Yolanda Bolea, Alberto Sanfeliu

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Mobile robots can be used in many different applications, including mapping, search, rescue, reconnaissance, hazard detection, and carpet cleaning, exploration, etc. However, they are limited due to their reliance on traditional energy sources such as electricity and oil which cannot always provide a convenient energy source in all situations. In an ever more eco-conscious world, solar energy offers the most environmentally clean option of all energy sources. Electricity presents threats of pollution resulting from its production process, and oil poses a huge threat to the environment. Not only does it pose harm by the toxic emissions (for instance CO2 emissions), it produces the combustion process necessary to produce energy, but there is the ever present risk of oil spillages and damages to ecosystems. Solar energy can help to mitigate carbon emissions by replacing more carbon intensive sources of heat and power. The challenge of this work is to propose the design and the implementation of electric battery recharge stations. Those recharge docks are based on the use of renewable energy such as solar energy (with photovoltaic panels) with the object to reduce the CO2 emissions. In this paper, a comparative study of the CO2 emission productions (from the use of different energy sources: natural gas, gas oil, fuel and solar panels) in the charging process of the Segway PT batteries is carried out. To make the study with solar energy, a photovoltaic panel, and a Buck-Boost DC/DC block has been used. Specifically, the STP005S-12/Db solar panel has been used to carry out our experiments. This module is a 5Wp-photovoltaic (PV) module, configured with 36 monocrystalline cells serially connected. With those elements, a battery recharge station is made to recharge the robot batteries. For the energy storage DC/DC block, a series of ultracapacitors have been used. Due to the variation of the PV panel with the temperature and irradiation, and the non-integer behavior of the ultracapacitors as well as the non-linearities of the whole system, authors have been used a fractional control method to achieve that solar panels supply the maximum allowed power to recharge the robots in the lesser time. Greenhouse gas emissions for production of electricity vary due to regional differences in source fuel. The impact of an energy technology on the climate can be characterised by its carbon emission intensity, a measure of the amount of CO2, or CO2 equivalent emitted by unit of energy generated. In our work, the coal is the fossil energy more hazardous, providing a 53% more of gas emissions than natural gas and a 30% more than fuel. Moreover, it is remarkable that existing fossil fuel technologies produce high carbon emission intensity through the combustion of carbon-rich fuels, whilst renewable technologies such as solar produce little or no emissions during operation, but may incur emissions during manufacture. The solar energy thus can help to mitigate carbon emissions.

Keywords: autonomous robots, CO2 emissions, DC/DC buck-boost, solar energy

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41 Product Life Cycle Assessment of Generatively Designed Furniture for Interiors Using Robot Based Additive Manufacturing

Authors: Andrew Fox, Qingping Yang, Yuanhong Zhao, Tao Zhang

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Furniture is a very significant subdivision of architecture and its inherent interior design activities. The furniture industry has developed from an artisan-driven craft industry, whose forerunners saw themselves manifested in their crafts and treasured a sense of pride in the creativity of their designs, these days largely reduced to an anonymous collective mass-produced output. Although a very conservative industry, there is great potential for the implementation of collaborative digital technologies allowing a reconfigured artisan experience to be reawakened in a new and exciting form. The furniture manufacturing industry, in general, has been slow to adopt new methodologies for a design using artificial and rule-based generative design. This tardiness has meant the loss of potential to enhance its capabilities in producing sustainable, flexible, and mass customizable ‘right first-time’ designs. This paper aims to demonstrate the concept methodology for the creation of alternative and inspiring aesthetic structures for robot-based additive manufacturing (RBAM). These technologies can enable the economic creation of previously unachievable structures, which traditionally would not have been commercially economic to manufacture. The integration of these technologies with the computing power of generative design provides the tools for practitioners to create concepts which are well beyond the insight of even the most accomplished traditional design teams. This paper aims to address the problem by introducing generative design methodologies employing the Autodesk Fusion 360 platform. Examination of the alternative methods for its use has the potential to significantly reduce the estimated 80% contribution to environmental impact at the initial design phase. Though predominantly a design methodology, generative design combined with RBAM has the potential to leverage many lean manufacturing and quality assurance benefits, enhancing the efficiency and agility of modern furniture manufacturing. Through a case study examination of a furniture artifact, the results will be compared to a traditionally designed and manufactured product employing the Ecochain Mobius product life cycle analysis (LCA) platform. This will highlight the benefits of both generative design and robot-based additive manufacturing from an environmental impact and manufacturing efficiency standpoint. These step changes in design methodology and environmental assessment have the potential to revolutionise the design to manufacturing workflow, giving momentum to the concept of conceiving a pre-industrial model of manufacturing, with the global demand for a circular economy and bespoke sustainable design at its heart.

Keywords: robot, manufacturing, generative design, sustainability, circular econonmy, product life cycle assessment, furniture

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40 Adapting Cyber Physical Production Systems to Small and Mid-Size Manufacturing Companies

Authors: Yohannes Haile, Dipo Onipede, Jr., Omar Ashour

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The main thrust of our research is to determine Industry 4.0 readiness of small and mid-size manufacturing companies in our region and assist them to implement Cyber Physical Production System (CPPS) capabilities. Adopting CPPS capabilities will help organizations realize improved quality, order delivery, throughput, new value creation, and reduced idle time of machines and work centers of their manufacturing operations. The key metrics for the assessment include the level of intelligence, internal and external connections, responsiveness to internal and external environmental changes, capabilities for customization of products with reference to cost, level of additive manufacturing, automation, and robotics integration, and capabilities to manufacture hybrid products in the near term, where near term is defined as 0 to 18 months. In our initial evaluation of several manufacturing firms which are profitable and successful in what they do, we found low level of Physical-Digital-Physical (PDP) loop in their manufacturing operations, whereas 100% of the firms included in this research have specialized manufacturing core competencies that have differentiated them from their competitors. The level of automation and robotics integration is low to medium range, where low is defined as less than 30%, and medium is defined as 30 to 70% of manufacturing operation to include automation and robotics. However, there is a significant drive to include these capabilities at the present time. As it pertains to intelligence and connection of manufacturing systems, it is observed to be low with significant variance in tying manufacturing operations management to Enterprise Resource Planning (ERP). Furthermore, it is observed that the integration of additive manufacturing in general, 3D printing, in particular, to be low, but with significant upside of integrating it in their manufacturing operations in the near future. To hasten the readiness of the local and regional manufacturing companies to Industry 4.0 and transitions towards CPPS capabilities, our working group (ADMAR Working Group) in partnership with our university have been engaged with the local and regional manufacturing companies. The goal is to increase awareness, share know-how and capabilities, initiate joint projects, and investigate the possibility of establishing the Center for Cyber Physical Production Systems Innovation (C2P2SI). The center is intended to support the local and regional university-industry research of implementing intelligent factories, enhance new value creation through disruptive innovations, the development of hybrid and data enhanced products, and the creation of digital manufacturing enterprises. All these efforts will enhance local and regional economic development and educate students that have well developed knowledge and applications of cyber physical manufacturing systems and Industry 4.0.

Keywords: automation, cyber-physical production system, digital manufacturing enterprises, disruptive innovation, new value creation, physical-digital-physical loop

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39 Efficiency of Different Types of Addition onto the Hydration Kinetics of Portland Cement

Authors: Marine Regnier, Pascal Bost, Matthieu Horgnies

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Some of the problems to be solved for the concrete industry are linked to the use of low-reactivity cement, the hardening of concrete under cold-weather and the manufacture of pre-casted concrete without costly heating step. The development of these applications needs to accelerate the hydration kinetics, in order to decrease the setting time and to obtain significant compressive strengths as soon as possible. The mechanisms enhancing the hydration kinetics of alite or Portland cement (e.g. the creation of nucleation sites) were already studied in literature (e.g. by using distinct additions such as titanium dioxide nanoparticles, calcium carbonate fillers, water-soluble polymers, C-S-H, etc.). However, the goal of this study was to establish a clear ranking of the efficiency of several types of additions by using a robust and reproducible methodology based on isothermal calorimetry (performed at 20°C). The cement was a CEM I 52.5N PM-ES (Blaine fineness of 455 m²/kg). To ensure the reproducibility of the experiments and avoid any decrease of the reactivity before use, the cement was stored in waterproof and sealed bags to avoid any contact with moisture and carbon dioxide. The experiments were performed on Portland cement pastes by using a water-to-cement ratio of 0.45, and incorporating different compounds (industrially available or laboratory-synthesized) that were selected according to their main composition and their specific surface area (SSA, calculated using the Brunauer-Emmett-Teller (BET) model and nitrogen adsorption isotherms performed at 77K). The intrinsic effects of (i) dry powders (e.g. fumed silica, activated charcoal, nano-precipitates of calcium carbonate, afwillite germs, nanoparticles of iron and iron oxides , etc.), and (ii) aqueous solutions (e.g. containing calcium chloride, hydrated Portland cement or Master X-SEED 100, etc.) were investigated. The influence of the amount of addition, calculated relatively to the dry extract of each addition compared to cement (and by conserving the same water-to-cement ratio) was also studied. The results demonstrated that the X-SEED®, the hydrated calcium nitrate, the calcium chloride (and, at a minor level, a solution of hydrated Portland cement) were able to accelerate the hydration kinetics of Portland cement, even at low concentration (e.g. 1%wt. of dry extract compared to cement). By using higher rates of additions, the fumed silica, the precipitated calcium carbonate and the titanium dioxide can also accelerate the hydration. In the case of the nano-precipitates of calcium carbonate, a correlation was established between the SSA and the accelerating effect. On the contrary, the nanoparticles of iron or iron oxides, the activated charcoal and the dried crystallised hydrates did not show any accelerating effect. Future experiments will be scheduled to establish the ranking of these additions, in terms of accelerating effect, by using low-reactivity cements and other water to cement ratios.

Keywords: acceleration, hydration kinetics, isothermal calorimetry, Portland cement

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38 Mechanism of Veneer Colouring for Production of Multilaminar Veneer from Plantation-Grown Eucalyptus Globulus

Authors: Ngoc Nguyen

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There is large plantation of Eucalyptus globulus established which has been grown to produce pulpwood. This resource is not suitable for the production of decorative products, principally due to low grades of wood and “dull” appearance but many trials have been already undertaken for the production of veneer and veneer-based engineered wood products, such as plywood and laminated veneer lumber (LVL). The manufacture of veneer-based products has been recently identified as an unprecedented opportunity to promote higher value utilisation of plantation resources. However, many uncertainties remain regarding the impacts of inferior wood quality of young plantation trees on product recovery and value, and with respect to optimal processing techniques. Moreover, the quality of veneer and veneer-based products is far from optimal as trees are young and have small diameters; and the veneers have the significant colour variation which affects to the added value of final products. Developing production methods which would enhance appearance of low-quality veneer would provide a great potential for the production of high-value wood products such as furniture, joinery, flooring and other appearance products. One of the methods of enhancing appearance of low quality veneer, developed in Italy, involves the production of multilaminar veneer, also named “reconstructed veneer”. An important stage of the multilaminar production is colouring the veneer which can be achieved by dyeing veneer with dyes of different colours depending on the type of appearance products, their design and market demand. Although veneer dyeing technology has been well advanced in Italy, it has been focused on poplar veneer from plantation which wood is characterized by low density, even colour, small amount of defects and high permeability. Conversely, the majority of plantation eucalypts have medium to high density, have a lot of defects, uneven colour and low permeability. Therefore, detailed study is required to develop dyeing methods suitable for colouring eucalypt veneers. Brown reactive dye is used for veneer colouring process. Veneers from sapwood and heartwood of two moisture content levels are used to conduct colouring experiments: green veneer and veneer dried to 12% MC. Prior to dyeing, all samples are treated. Both soaking (dipping) and vacuum pressure methods are used in the study to compare the results and select most efficient method for veneer dyeing. To date, the results of colour measurements by CIELAB colour system showed significant differences in the colour of the undyed veneers produced from heartwood part. The colour became moderately darker with increasing of Sodium chloride, compared to control samples according to the colour measurements. It is difficult to conclude a suitable dye solution used in the experiments at this stage as the variables such as dye concentration, dyeing temperature or dyeing time have not been done. The dye will be used with and without UV absorbent after all trials are completed using optimal parameters in colouring veneers.

Keywords: Eucalyptus globulus, veneer colouring/dyeing, multilaminar veneer, reactive dye

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37 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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36 Field Performance of Cement Treated Bases as a Reflective Crack Mitigation Technique for Flexible Pavements

Authors: Mohammad R. Bhuyan, Mohammad J. Khattak

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Deterioration of flexible pavements due to crack reflection from its soil-cement base layer is a major concern around the globe. The service life of flexible pavement diminishes significantly because of the reflective cracks. Highway agencies are struggling for decades to prevent or mitigate these cracks in order to increase pavement service lives. The root cause of reflective cracks is the shrinkage crack which occurs in the soil-cement bases during the cement hydration process. The primary factor that causes the shrinkage is the cement content of the soil-cement mixture. With the increase of cement content, the soil-cement base gains strength and durability, which is necessary to withstand the traffic loads. But at the same time, higher cement content creates more shrinkage resulting in more reflective cracks in pavements. Historically, various states of USA have used the soil-cement bases for constructing flexile pavements. State of Louisiana (USA) had been using 8 to 10 percent of cement content to manufacture the soil-cement bases. Such traditional soil-cement bases yield 2.0 MPa (300 psi) 7-day compressive strength and are termed as cement stabilized design (CSD). As these CSD bases generate significant reflective cracks, another design of soil-cement base has been utilized by adding 4 to 6 percent of cement content called cement treated design (CTD), which yields 1.0 MPa (150 psi) 7-day compressive strength. The reduction of cement content in the CTD base is expected to minimize shrinkage cracks thus increasing pavement service lives. Hence, this research study evaluates the long-term field performance of CTD bases with respect to CSD bases used in flexible pavements. Pavement Management System of the state of Louisiana was utilized to select flexible pavement projects with CSD and CTD bases that had good historical record and time-series distress performance data. It should be noted that the state collects roughness and distress data for 1/10th mile section every 2-year period. In total, 120 CSD and CTD projects were analyzed in this research, where more than 145 miles (CTD) and 175 miles (CSD) of roadways data were accepted for performance evaluation and benefit-cost analyses. Here, the service life extension and area based on distress performance were considered as benefits. It was found that CTD bases increased 1 to 5 years of pavement service lives based on transverse cracking as compared to CSD bases. On the other hand, the service lives based on longitudinal and alligator cracking, rutting and roughness index remain the same. Hence, CTD bases provide some service life extension (2.6 years, on average) to the controlling distress; transverse cracking, but it was inexpensive due to its lesser cement content. Consequently, CTD bases become 20% more cost-effective than the traditional CSD bases, when both bases were compared by net benefit-cost ratio obtained from all distress types.

Keywords: cement treated base, cement stabilized base, reflective cracking , service life, flexible pavement

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35 The Effect of Rice Husk Ash on the Mechanical and Durability Properties of Concrete

Authors: Binyamien Rasoul

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Portland cement is one of the most widely used construction materials in the world today; however, manufacture of ordinary Portland cement (OPC) emission significant amount of CO2 resulting environmental impact. On the other hand, rice husk ash (RHA), which is produce as by product material is generally considered to be an environmental issue as a waste material. This material (RHA) consists of non-crystalline silicon dioxide with high specific surface area and high pozzolanic reactivity. These RHA properties can demonstrate a significant influence in improving the mechanical and durability properties of mortar and concrete. Furthermore, rice husk ash can provide a cost effective and give concrete more sustainability. In this paper, chemical composition, reactive silica and fineness effect was assessed by examining five different types of RHA. Mortars and concrete specimens were molded with 5% to 50% of ash, replacing the Portland cement, and measured their compressive and tensile strength behavior. Beyond it, another two parameters had been considered: the durability of concrete blended RHA, and effect of temperature on the transformed of amorphous structure to crystalline form. To obtain the rice husk ash properties, these different types were subjected to X-Ray fluorescence to determine the chemical composition, while pozzolanic activity obtained by using X-Ray diffraction test. On the other hand, finesses and specific surface area were obtained by used Malvern Mastersizer 2000 test. The measured parameters properties of fresh mortar and concrete obtained by used flow table and slump test. While, for hardened mortar and concrete the compressive and tensile strength determined pulse the chloride ions penetration for concrete using NT Build 492 (Nord Test) – non-steady state migration test (RMT Test). The obtained test results indicated that RHA can be used as a cement replacement material in concrete with considerable proportion up to 50% percentages without compromising concrete strength. The use of RHA in the concrete as blending materials improved the different characteristics of the concrete product. The paper concludes that to exhibits a good compressive strength of OPC mortar or concrete with increase RHA replacement ratio rice husk ash should be consist of high silica content with high pozzolanic activity. Furthermore, with high amount of carbon content (12%) could be improve the strength of concrete when the silica structure is totally amorphous. As well RHA with high amount of crystalline form (25%) can be used as cement replacement when the silica content over 90%. The workability and strength of concrete increased by used of superplasticizer and it depends on the silica structure and carbon content. This study therefore is an investigation of the effect of partially replacing Ordinary Portland cement (OPC) with Rice hush Ash (RHA) on the mechanical properties and durability of concrete. This paper gives satisfactory results to use RHA in sustainable construction in order to reduce the carbon footprint associated with cement industry.

Keywords: OPC, ordinary Portland cement, RHA rice husk ash, W/B water to binder ratio, CO2, carbon dioxide

Procedia PDF Downloads 165
34 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

Procedia PDF Downloads 116
33 Electroactive Fluorene-Based Polymer Films Obtained by Electropolymerization

Authors: Mariana-Dana Damaceanu

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Electrochemical oxidation is one of the most convenient ways to obtain conjugated polymer films as polypyrrole, polyaniline, polythiophene or polycarbazole. The research in the field has been mainly directed to the study of electrical conduction properties of the materials obtained by electropolymerization, often the main reason being their use as electroconducting electrodes, and very little attention has been paid to the morphological and optical quality of the films electrodeposited on flat surfaces. Electropolymerization of the monomer solution was scarcely used in the past to manufacture polymer-based light-emitting diodes (PLED), most probably due to the difficulty of obtaining defectless polymer films with good mechanical and optical properties, or conductive polymers with well controlled molecular weights. Here we report our attempts in using electrochemical deposition as appropriate method for preparing ultrathin films of fluorene-based polymers for PLED applications. The properties of these films were evaluated in terms of structural morphology, optical properties, and electrochemical conduction. Thus, electropolymerization of 4,4'-(9-fluorenylidene)-dianiline was performed in dichloromethane solution, at a concentration of 10-2 M, using 0.1 M tetrabutylammonium tetrafluoroborate as electrolyte salt. The potential was scanned between 0 and 1.3 V on the one hand, and 0 - 2 V on the other hand, when polymer films with different structures and properties were obtained. Indium tin oxide-coated glass substrate of different size was used as working electrode, platinum wire as counter electrode and calomel electrode as reference. For each potential range 100 cycles were recorded at a scan rate of 100 mV/s. The film obtained in the potential range from 0 to 1.3 V, namely poly(FDA-NH), is visible to the naked eye, being light brown, transparent and fluorescent, and displays an amorphous morphology. Instead, the electrogrowth poly(FDA) film in the potential range of 0 - 2 V is yellowish-brown and opaque, presenting a self-assembled structure in aggregates of irregular shape and size. The polymers structure was identified by FTIR spectroscopy, which shows the presence of broad bands specific to a polymer, the band centered at approx. 3443 cm-1 being ascribed to the secondary amine. The two polymer films display two absorption maxima, at 434-436 nm assigned to π-π* transitions of polymers, and another at 832 and 880 nm assigned to polaron transitions. The fluorescence spectra indicated the presence of emission bands in the blue domain, with two peaks at 422 and 488 nm for poly (FDA-NH), and four narrow peaks at 422, 447, 460 and 484 nm for poly(FDA), peaks originating from fluorene-containing segments of varying degrees of conjugation. Poly(FDA-NH) exhibited two oxidation peaks in the anodic region and the HOMO energy value of 5.41 eV, whereas poly(FDA) showed only one oxidation peak and the HOMO level localized at 5.29 eV. The electrochemical data are discussed in close correlation with the proposed chemical structure of the electrogrowth films. Further research will be carried out to study their use and performance in light-emitting devices.

Keywords: electrogrowth polymer films, fluorene, morphology, optical properties

Procedia PDF Downloads 319
32 A Reusable Foundation Solution for Onshore Windmills

Authors: Wael Mohamed, Per-Erik Austrell, Ola Dahlblom

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Wind farms repowering is a significant topic nowadays. Wind farms repowering means the complete dismantling of the existing turbine, tower and foundation at an existing site and replacing these units with taller and larger units. Modern wind turbines are designed to withstand approximately for 20~25 years. However, a very long design life of 100 years or more can be expected for high-quality concrete foundations. Based on that there are significant economic and environmental benefits of replacing the out-of-date wind turbine with a new turbine of better power generation capacity and reuse the foundation. The big difference in lifetime shows a potential for new foundation solution to allow wind farms to be updated with taller and larger units in order to increase the energy production. This also means a significant change in the design loads on the foundations. Therefore, the new foundation solution should be able to handle the additional overturning loads. A raft surrounded by an active stabilisation system is proposed in this study. The concept of an active stabilisation system is a novel idea using a movable load to stabilise against the overturning moment. The active stabilisation system consists of a water tank being divided into eight compartments. The system uses the water as a movable load by pumping it into two compartments to stabilise against the overturning moment. The position of the water will rely on the wind direction and a water movement system depending on a number of electric motors and pipes with electric valves is used. One of the advantages of this active foundation solution is that some cost-efficient adjustment could be done to make this foundation able to support larger and taller units. After the end of the first turbine lifetime, an option is presented here to reuse this foundation and make it able to support taller and larger units. This option is considered using extra water volume to fill four compartments instead of two compartments. This extra water volume will increase the stability moment by 41% compared to using water in two compartments. The geotechnical performance of the new foundation solution is investigated using two existing weak soil profiles in Egypt and Sweden. A comparative study of the new solution and a piled raft with long friction piles is performed using finite element simulations. The results show that using a raft surrounded by an active stabilisation system decreases the tilting compared to a piled raft with friction piles. Moreover, it is found that using a raft surrounded by an active stabilisation system decreases the foundation costs compared to a piled raft with friction piles. In term of the environmental impact, it is found that the new foundation has a beneficial impact on the CO2 emissions. It saves roughly from 296.1 tonnes-CO2 to 518.21 tonnes-CO2 from the manufacture of concrete if the new foundation solution is used for another turbine-lifetime.

Keywords: active stabilisation system, CO2 emissions, FE analysis, reusable, weak soils

Procedia PDF Downloads 190
31 Colonizing the Colonizers: Layers of Subjectification in the Russian Caucasus

Authors: Aaron Derner

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Unlike the histories of France, the UK, or even Spain, the Russian colonial past often dissolves before the seemingly more salient Cold War figurations or Soviet dissolution. The obvious explanation behind Caucasian states’ roles—that of Russian-propped governments obeying the whims of their patron—is but the latest instance of such oversight. Where the results of colonial social and cultural interactions are indelibly stamped across France, Algeria, and every other former (and current) French holding, so to are the Muscovite and Russian colonial ambitions embedded within the modern politics and cultures of both Russia and the Caucasus. Russian colonial artefacts are enhanced and perhaps granted an additional social explanatory edge over those of the ‘typical’ colonizers, by the cyclical adoration for and noisy rejection of European cultural markers over the centuries, along with the somewhat unusual composition of the Cossacks: Russia’s main agents of colonialization within the Caucasian frontier. The story of Russia and Chechnya, of all the Caucasus, is of the manufacture of social and individual identity through “modes of subjectification” inherent within the region’s colonial history and driven by the triangular interactions between three main groups: the Cossacks, the Caucasian Mountain Tribes, and the Russian Metropol. Together, interactions between these social groups worked to shape and transform the lifestyles and institutional pathologies that constitute the Russian and Chechen states and the politics between them. At the core of this (Western) state-building is the simultaneous and seemingly contradictory desire to be more Western and emulate Western cultural and political practices while also desperately grasping for a uniquely Russian identity. This sits somewhat ironically against the backdrop that Russia hosted a frontier-based settler society and had established that distinctly European feature of settler colonialism early in its history—arguably establishing a claim to being the most “colonial” of the colonial powers. There is no doubt that these forces worked to shape contemporary Russian political and social identity—apparent in the mythic popularity of the Cossack in Russian literature, politics, and academic discourse. What needs to be expanded from the current narrative, however, is that beyond the Cossack identity’s attractiveness on the grounds of its tones of freedom and resistance to unjust authority, the identity is rooted in the imperial ambitions and colonial experiences of the Russian state, and is, therefore, a direct marker of domination and subjectification. Adding an unusual dimension to this not-uncommon cultural progression, the Russian state needed to colonize both the Caucases and the Russian Cossacks, appropriating them in much the same way they appropriated the Circassian mountain tribes. The focus of this paper is not to tell yet another story of how one culture entered an area to overpower another but how a ‘powerful,’ ‘modern,’ ‘Western(ish)’ culture was profoundly and continually changed through its contact with a group of tribal ‘savages’ and ‘braves.’

Keywords: Russia, chechnya, subjectification, caucasus, cossacks, Ukraine

Procedia PDF Downloads 47
30 A Greener Approach towards the Synthesis of an Antimalarial Drug Lumefantrine

Authors: Luphumlo Ncanywa, Paul Watts

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Malaria is a disease that kills approximately one million people annually. Children and pregnant women in sub-Saharan Africa lost their lives due to malaria. Malaria continues to be one of the major causes of death, especially in poor countries in Africa. Decrease the burden of malaria and save lives is very essential. There is a major concern about malaria parasites being able to develop resistance towards antimalarial drugs. People are still dying due to lack of medicine affordability in less well-off countries in the world. If more people could receive treatment by reducing the cost of drugs, the number of deaths in Africa could be massively reduced. There is a shortage of pharmaceutical manufacturing capability within many of the countries in Africa. However one has to question how Africa would actually manufacture drugs, active pharmaceutical ingredients or medicines developed within these research programs. It is quite likely that such manufacturing would be outsourced overseas, hence increasing the cost of production and potentially limiting the full benefit of the original research. As a result the last few years has seen major interest in developing more effective and cheaper technology for manufacturing generic pharmaceutical products. Micro-reactor technology (MRT) is an emerging technique that enables those working in research and development to rapidly screen reactions utilizing continuous flow, leading to the identification of reaction conditions that are suitable for usage at a production level. This emerging technique will be used to develop antimalarial drugs. It is this system flexibility that has the potential to reduce both the time was taken and risk associated with transferring reaction methodology from research to production. Using an approach referred to as scale-out or numbering up, a reaction is first optimized within the laboratory using a single micro-reactor, and in order to increase production volume, the number of reactors employed is simply increased. The overall aim of this research project is to develop and optimize synthetic process of antimalarial drugs in the continuous processing. This will provide a step change in pharmaceutical manufacturing technology that will increase the availability and affordability of antimalarial drugs on a worldwide scale, with a particular emphasis on Africa in the first instance. The research will determine the best chemistry and technology to define the lowest cost manufacturing route to pharmaceutical products. We are currently developing a method to synthesize Lumefantrine in continuous flow using batch process as bench mark. Lumefantrine is a dichlorobenzylidine derivative effective for the treatment of various types of malaria. Lumefantrine is an antimalarial drug used with artemether for the treatment of uncomplicated malaria. The results obtained when synthesizing Lumefantrine in a batch process are transferred into a continuous flow process in order to develop an even better and reproducible process. Therefore, development of an appropriate synthetic route for Lumefantrine is significant in pharmaceutical industry. Consequently, if better (and cheaper) manufacturing routes to antimalarial drugs could be developed and implemented where needed, it is far more likely to enable antimalarial drugs to be available to those in need.

Keywords: antimalarial, flow, lumefantrine, synthesis

Procedia PDF Downloads 164
29 Aspects Concerning the Use of Recycled Concrete Aggregates

Authors: Ion Robu, Claudiu Mazilu, Radu Deju

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Natural aggregates (gravel and crushed) are essential non-renewable resources which are used for infrastructure works and civil engineering. In European Union member states from Southeast Europe, it is estimated that the construction industry will grow by 4.2% thereafter complicating aggregate supply management. In addition, a significant additional problem that can be associated to the aggregates industry is wasting potential resources through waste dumping of inert waste, especially waste from construction and demolition activities. In 2012, in Romania, less than 10% of construction and demolition waste (including concrete) are valorized, while the European Union requires that by 2020 this proportion should be at least 70% (Directive 2008/98/EC on waste, transposed into Romanian legislation by Law 211/2011). Depending on the efficiency of waste processing and the quality of recycled aggregate concrete (RCA) obtained, poor quality aggregate can be used as foundation material for roads and at the high quality for new concrete on construction. To obtain good quality concrete using recycled aggregate is necessary to meet the minimum requirements defined by the rules for the manufacture of concrete with natural aggregate. Properties of recycled aggregate (density, granulosity, granule shape, water absorption, weight loss to Los Angeles test, attached mortar content etc.) are the basis for concrete quality; also establishing appropriate proportions between components and the concrete production methods are extremely important for its quality. This paper presents a study on the use of recycled aggregates, from a concrete of specified class, to acquire new cement concrete with different percentages of recycled aggregates. To achieve recycled aggregates several batches of concrete class C16/20, C25/30 and C35/45 were made, the compositions calculation being made according NE012/2007 CP012/2007. Tests for producing recycled aggregate was carried out using concrete samples of the established three classes after 28 days of storage under the above conditions. Cubes with 150mm side were crushed in a first stage with a jaw crusher Liebherr type set at 50 mm nominally. The resulting material was separated by sieving on granulometric sorts and 10-50 sort was used for preliminary tests of crushing in the second stage with a jaw crusher BB 200 Retsch model, respectively a hammer crusher Buffalo Shuttle WA-12-H model. It was highlighted the influence of the type of crusher used to obtain recycled aggregates on granulometry and granule shape and the influence of the attached mortar on the density, water absorption, behavior to the Los Angeles test etc. The proportion of attached mortar was determined and correlated with provenance concrete class of the recycled aggregates and their granulometric sort. The aim to characterize the recycled aggregates is their valorification in new concrete used in construction. In this regard have been made a series of concrete in which the recycled aggregate content was varied from 0 to 100%. The new concrete were characterized by point of view of the change in the density and compressive strength with the proportion of recycled aggregates. It has been shown that an increase in recycled aggregate content not necessarily mean a reduction in compressive strength, quality of the aggregate having a decisive role.

Keywords: recycled concrete aggregate, characteristics, recycled aggregate concrete, properties

Procedia PDF Downloads 182
28 Highly Selective Phosgene Free Synthesis of Methylphenylcarbamate from Aniline and Dimethyl Carbonate over Heterogeneous Catalyst

Authors: Nayana T. Nivangune, Vivek V. Ranade, Ashutosh A. Kelkar

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Organic carbamates are versatile compounds widely employed as pesticides, fungicides, herbicides, dyes, pharmaceuticals, cosmetics and in the synthesis of polyurethanes. Carbamates can be easily transformed into isocyanates by thermal cracking. Isocyantes are used as precursors for manufacturing agrochemicals, adhesives and polyurethane elastomers. Manufacture of polyurethane foams is a major application of aromatic ioscyanates and in 2007 the global consumption of polyurethane was about 12 million metric tons/year and the average annual growth rate was about 5%. Presently Isocyanates/carbamates are manufactured by phosgene based process. However, because of high toxicity of phoegene and formation of waste products in large quantity; there is a need to develop alternative and safer process for the synthesis of isocyanates/carbamates. Recently many alternative processes have been investigated and carbamate synthesis by methoxycarbonylation of aromatic amines using dimethyl carbonate (DMC) as a green reagent has emerged as promising alternative route. In this reaction methanol is formed as a by-product, which can be converted to DMC either by oxidative carbonylation of methanol or by reacting with urea. Thus, the route based on DMC has a potential to provide atom efficient and safer route for the synthesis of carbamates from DMC and amines. Lot of work is being carried out on the development of catalysts for this reaction and homogeneous zinc salts were found to be good catalysts for the reaction. However, catalyst/product separation is challenging with these catalysts. There are few reports on the use of supported Zn catalysts; however, deactivation of the catalyst is the major problem with these catalysts. We wish to report here methoxycarbonylation of aniline to methylphenylcarbamate (MPC) using amino acid complexes of Zn as highly active and selective catalysts. The catalysts were characterized by XRD, IR, solid state NMR and XPS analysis. Methoxycarbonylation of aniline was carried out at 170 °C using 2.5 wt% of the catalyst to achieve >98% conversion of aniline with 97-99% selectivity to MPC as the product. Formation of N-methylated products in small quantity (1-2%) was also observed. Optimization of the reaction conditions was carried out using zinc-proline complex as the catalyst. Selectivity was strongly dependent on the temperature and aniline:DMC ratio used. At lower aniline:DMC ratio and at higher temperature, selectivity to MPC decreased (85-89% respectively) with the formation of N-methylaniline (NMA), N-methyl methylphenylcarbamate (MMPC) and N,N-dimethyl aniline (NNDMA) as by-products. Best results (98% aniline conversion with 99% selectivity to MPC in 4 h) were observed at 170oC and aniline:DMC ratio of 1:20. Catalyst stability was verified by carrying out recycle experiment. Methoxycarbonylation preceded smoothly with various amine derivatives indicating versatility of the catalyst. The catalyst is inexpensive and can be easily prepared from zinc salt and naturally occurring amino acids. The results are important and provide environmentally benign route for MPC synthesis with high activity and selectivity.

Keywords: aniline, heterogeneous catalyst, methoxycarbonylation, methylphenyl carbamate

Procedia PDF Downloads 249
27 Fuels and Platform Chemicals Production from Lignocellulosic Biomass: Current Status and Future Prospects

Authors: Chandan Kundu, Sankar Bhattacharya

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A significant disadvantage of fossil fuel energy production is the considerable amount of carbon dioxide (CO₂) released, which is one of the contributors to climate change. Apart from environmental concerns, changing fossil fuel prices have pushed society gradually towards renewable energy sources in recent years. Biomass is a plentiful and renewable resource and a source of carbon. Recent years have seen increased research interest in generating fuels and chemicals from biomass. Unlike fossil-based resources, biomass is composed of lignocellulosic material, which does not contribute to the increase in atmospheric CO₂ over a longer term. These considerations contribute to the current move of the chemical industry from non-renewable feedstock to renewable biomass. This presentation focuses on generating bio-oil and two major platform chemicals that can potentially improve the environment. Thermochemical processes such as pyrolysis are considered viable methods for producing bio-oil and biomass-based platform chemicals. Fluidized bed reactors, on the other hand, are known to boost bio-oil yields during pyrolysis due to their superior mixing and heat transfer features, as well as their scalability. This review and the associated experimental work are focused on the thermochemical conversion of biomass to bio-oil and two high-value platform chemicals, Levoglucosenone (LGO) and 5-Chloromethyl furfural (5-CMF), in a fluidized bed reactor. These two active molecules with distinct features can potentially be useful monomers in the chemical and pharmaceutical industries since they are well adapted to the manufacture of biologically active products. This process took several meticulous steps. To begin, the biomass was delignified using a peracetic acid pretreatment to remove lignin. Because of its complicated structure, biomass must be pretreated to remove the lignin, increasing access to the carbohydrate components and converting them to platform chemicals. The biomass was then characterized by Thermogravimetric analysis, Synchrotron-based THz spectroscopy, and in-situ DRIFTS in the laboratory. Based on the results, a continuous-feeding fluidized bed reactor system was constructed to generate platform chemicals from pretreated biomass using hydrogen chloride acid-gas as a catalyst. The procedure also yields biochar, which has a number of potential applications, including soil remediation, wastewater treatment, electrode production, and energy resource utilization. Consequently, this research also includes a preliminary experimental evaluation of the biochar's prospective applications. The biochar obtained was evaluated for its CO₂ and steam reactivity. The outline of the presentation will comprise the following: Biomass pretreatment for effective delignification Mechanistic study of the thermal and thermochemical conversion of biomass Thermochemical conversion of untreated and pretreated biomass in the presence of an acid catalyst to produce LGO and CMF A thermo-catalytic process for the production of LGO and 5-CMF in a continuously-fed fluidized bed reactor and efficient separation of chemicals Use of biochar generated from the platform chemicals production through gasification

Keywords: biomass, pretreatment, pyrolysis, levoglucosenone

Procedia PDF Downloads 95
26 Self-Organizing Maps for Exploration of Partially Observed Data and Imputation of Missing Values in the Context of the Manufacture of Aircraft Engines

Authors: Sara Rejeb, Catherine Duveau, Tabea Rebafka

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To monitor the production process of turbofan aircraft engines, multiple measurements of various geometrical parameters are systematically recorded on manufactured parts. Engine parts are subject to extremely high standards as they can impact the performance of the engine. Therefore, it is essential to analyze these databases to better understand the influence of the different parameters on the engine's performance. Self-organizing maps are unsupervised neural networks which achieve two tasks simultaneously: they visualize high-dimensional data by projection onto a 2-dimensional map and provide clustering of the data. This technique has become very popular for data exploration since it provides easily interpretable results and a meaningful global view of the data. As such, self-organizing maps are usually applied to aircraft engine condition monitoring. As databases in this field are huge and complex, they naturally contain multiple missing entries for various reasons. The classical Kohonen algorithm to compute self-organizing maps is conceived for complete data only. A naive approach to deal with partially observed data consists in deleting items or variables with missing entries. However, this requires a sufficient number of complete individuals to be fairly representative of the population; otherwise, deletion leads to a considerable loss of information. Moreover, deletion can also induce bias in the analysis results. Alternatively, one can first apply a common imputation method to create a complete dataset and then apply the Kohonen algorithm. However, the choice of the imputation method may have a strong impact on the resulting self-organizing map. Our approach is to address simultaneously the two problems of computing a self-organizing map and imputing missing values, as these tasks are not independent. In this work, we propose an extension of self-organizing maps for partially observed data, referred to as missSOM. First, we introduce a criterion to be optimized, that aims at defining simultaneously the best self-organizing map and the best imputations for the missing entries. As such, missSOM is also an imputation method for missing values. To minimize the criterion, we propose an iterative algorithm that alternates the learning of a self-organizing map and the imputation of missing values. Moreover, we develop an accelerated version of the algorithm by entwining the iterations of the Kohonen algorithm with the updates of the imputed values. This method is efficiently implemented in R and will soon be released on CRAN. Compared to the standard Kohonen algorithm, it does not come with any additional cost in terms of computing time. Numerical experiments illustrate that missSOM performs well in terms of both clustering and imputation compared to the state of the art. In particular, it turns out that missSOM is robust to the missingness mechanism, which is in contrast to many imputation methods that are appropriate for only a single mechanism. This is an important property of missSOM as, in practice, the missingness mechanism is often unknown. An application to measurements on one type of part is also provided and shows the practical interest of missSOM.

Keywords: imputation method of missing data, partially observed data, robustness to missingness mechanism, self-organizing maps

Procedia PDF Downloads 125
25 Nanoporous Activated Carbons for Fuel Cells and Supercapacitors

Authors: A. Volperts, G. Dobele, A. Zhurinsh, I. Kruusenberg, A. Plavniece, J. Locs

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Nowadays energy consumption constantly increases and development of effective and cheap electrochemical sources of power, such as fuel cells and electrochemical capacitors, is topical. Due to their high specific power, charge and discharge rates, working lifetime supercapacitor based energy accumulation systems are more and more extensively being used in mobile and stationary devices. Lignocellulosic materials are widely used as precursors and account for around 45% of the total raw materials used for the manufacture of activated carbon which is the most suitable material for supercapacitors. First part of our research is devoted to study of influence of main stages of wood thermochemical activation parameters on activated carbons porous structure formation. It was found that the main factors governing the properties of carbon materials are specific surface area, volume and pore size distribution, particles dispersity, ash content and oxygen containing groups content. Influence of activated carbons attributes on capacitance and working properties of supercapacitor are demonstrated. The correlation between activated carbons porous structure indices and electrochemical specifications of supercapacitors with electrodes made from these materials has been determined. It is shown that if synthesized activated carbons are used in supercapacitors then high specific capacitances can be reached – more than 380 F/g in 4.9M sulfuric acid based electrolytes and more than 170 F/g in 1 M tetraethylammonium tetrafluoroborate in acetonitrile electrolyte. Power specifications and minimal price of H₂-O₂ fuel cells are limited by the expensive platinum-based catalysts. The main direction in development of non-platinum catalysts for the oxygen reduction is the study of cheap porous carbonaceous materials which can be obtained by the pyrolysis of polymers including renewable biomass. It is known that nitrogen atoms in carbon materials to a high degree determine properties of the doped activated carbons, such as high electrochemical stability, hardness, electric resistance, etc. The lack of sufficient knowledge on the doping of the carbon materials calls for the ongoing researches of properties and structure of modified carbon matrix. In the second part of this study, highly porous activated carbons were synthesized using alkali thermochemical activation from wood, cellulose and cellulose production residues – craft lignin and sewage sludge. Activated carbon samples were doped with dicyandiamide and melamine for the application as fuel cell cathodes. Conditions of nitrogen introduction (solvent, treatment temperature) and its content in the carbonaceous material, as well as porous structure characteristics, such as specific surface and pore size distribution, were studied. It was found that efficiency of doping reaction depends on the elemental oxygen content in the activated carbon. Relationships between nitrogen content, porous structure characteristics and electrodes electrochemical properties are demonstrated.

Keywords: activated carbons, low-temperature fuel cells, nitrogen doping, porous structure, supercapacitors

Procedia PDF Downloads 92
24 Development and Evaluation of Economical Self-cleaning Cement

Authors: Anil Saini, Jatinder Kumar Ratan

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Now a day, the key issue for the scientific community is to devise the innovative technologies for sustainable control of urban pollution. In urban cities, a large surface area of the masonry structures, buildings, and pavements is exposed to the open environment, which may be utilized for the control of air pollution, if it is built from the photocatalytically active cement-based constructional materials such as concrete, mortars, paints, and blocks, etc. The photocatalytically active cement is formulated by incorporating a photocatalyst in the cement matrix, and such cement is generally known as self-cleaning cement In the literature, self-cleaning cement has been synthesized by incorporating nanosized-TiO₂ (n-TiO₂) as a photocatalyst in the formulation of the cement. However, the utilization of n-TiO₂ for the formulation of self-cleaning cement has the drawbacks of nano-toxicity, higher cost, and agglomeration as far as the commercial production and applications are concerned. The use of microsized-TiO₂ (m-TiO₂) in place of n-TiO₂ for the commercial manufacture of self-cleaning cement could avoid the above-mentioned problems. However, m-TiO₂ is less photocatalytically active as compared to n- TiO₂ due to smaller surface area, higher band gap, and increased recombination rate. As such, the use of m-TiO₂ in the formulation of self-cleaning cement may lead to a reduction in photocatalytic activity, thus, reducing the self-cleaning, depolluting, and antimicrobial abilities of the resultant cement material. So improvement in the photoactivity of m-TiO₂ based self-cleaning cement is the key issue for its practical applications in the present scenario. The current work proposes the use of surface-fluorinated m-TiO₂ for the formulation of self-cleaning cement to enhance its photocatalytic activity. The calcined dolomite, a constructional material, has also been utilized as co-adsorbent along with the surface-fluorinated m-TiO₂ in the formulation of self-cleaning cement to enhance the photocatalytic performance. The surface-fluorinated m-TiO₂, calcined dolomite, and the formulated self-cleaning cement were characterized using diffuse reflectance spectroscopy (DRS), X-ray diffraction analysis (XRD), field emission-scanning electron microscopy (FE-SEM), energy dispersive x-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), BET (Brunauer–Emmett–Teller) surface area, and energy dispersive X-ray fluorescence spectrometry (EDXRF). The self-cleaning property of the as-prepared self-cleaning cement was evaluated using the methylene blue (MB) test. The depolluting ability of the formulated self-cleaning cement was assessed through a continuous NOX removal test. The antimicrobial activity of the self-cleaning cement was appraised using the method of the zone of inhibition. The as-prepared self-cleaning cement obtained by uniform mixing of 87% clinker, 10% calcined dolomite, and 3% surface-fluorinated m-TiO₂ showed a remarkable self-cleaning property by providing 53.9% degradation of the coated MB dye. The self-cleaning cement also depicted a noteworthy depolluting ability by removing 5.5% of NOx from the air. The inactivation of B. subtiltis bacteria in the presence of light confirmed the significant antimicrobial property of the formulated self-cleaning cement. The self-cleaning, depolluting, and antimicrobial results are attributed to the synergetic effect of surface-fluorinated m-TiO₂ and calcined dolomite in the cement matrix. The present study opens an idea and route for further research for acile and economical formulation of self-cleaning cement.

Keywords: microsized-titanium dioxide (m-TiO₂), self-cleaning cement, photocatalysis, surface-fluorination

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23 Construction Port Requirements for Floating Wind Turbines

Authors: Alan Crowle, Philpp Thies

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As the floating offshore wind turbine industry continues to develop and grow, the capabilities of established port facilities need to be assessed as to their ability to support the expanding construction and installation requirements. This paper assesses current infrastructure requirements and projected changes to port facilities that may be required to support the floating offshore wind industry. Understanding the infrastructure needs of the floating offshore renewable industry will help to identify the port-related requirements. Floating Offshore Wind Turbines can be installed further out to sea and in deeper waters than traditional fixed offshore wind arrays, meaning that it can take advantage of stronger winds. Separate ports are required for substructure construction, fit-out of the turbines, moorings, subsea cables and maintenance. Large areas are required for the laydown of mooring equipment; inter-array cables, turbine blades and nacelles. The capabilities of established port facilities to support floating wind farms are assessed by evaluation of the size of substructures, the height of wind turbine with regards to the cranes for fitting of blades, distance to offshore site and offshore installation vessel characteristics. The paper will discuss the advantages and disadvantages of using large land-based cranes, inshore floating crane vessels or offshore crane vessels at the fit-out port for the installation of the turbine. Water depths requirements for import of materials and export of the completed structures will be considered. There are additional costs associated with any emerging technology. However part of the popularity of Floating Offshore Wind Turbines stems from the cost savings against permanent structures like fixed wind turbines. Floating Offshore Wind Turbine developers can benefit from lighter, more cost-effective equipment which can be assembled in port and towed to the site rather than relying on large, expensive installation vessels to transport and erect fixed bottom turbines. The ability to assemble Floating Offshore Wind Turbines equipment onshore means minimizing highly weather-dependent operations like offshore heavy lifts and assembly, saving time and costs and reducing safety risks for offshore workers. Maintenance might take place in safer onshore conditions for barges and semi-submersibles. Offshore renewables, such as floating wind, can take advantage of this wealth of experience, while oil and gas operators can deploy this experience at the same time as entering the renewables space The floating offshore wind industry is in the early stages of development and port facilities are required for substructure fabrication, turbine manufacture, turbine construction and maintenance support. The paper discusses the potential floating wind substructures as this provides a snapshot of the requirements at the present time, and potential technological developments required for commercial development. Scaling effects of demonstration-scale projects will be addressed, however, the primary focus will be on commercial-scale (30+ units) device floating wind energy farms.

Keywords: floating wind, port, marine construction, offshore renewables

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22 Natural Dyes: A Global Perspective on Commercial Solutions and Industry Players

Authors: Laura Seppälä, Ana Nuutinen

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Environmental concerns are increasing the interest in the potential uses of natural dyes. Natural dyes are more safe and environmentally friendly option than synthetic dyes. However, one must be also cautious with natural dyes, because, for example, some dyestuff such as plants or mushrooms, as well as some mordants are poisonous. By natural dyes we mean dyes that are derived from plants, fungi, bark, lichens, algae, insects, and minerals. Different plant parts, such as stems, leaves, flowers, roots, bark, berries, fruits, and cones, can be utilized for textile dyeing and printing, pigment manufacture, and other processes depending on the season. They may be utilized to produce distinctive colour tones that are challenging to do with synthetic dyes. This adds value to textiles and makes them stand out. Synthetic dyes quickly replaced natural dyes, after being developed in the middle of the 19th century, but natural dyes have remained the dyeing method of crafters until recently. This research examines the commercial solutions for natural dyes in many parts of the world, such as Europe, the United States, South America, Africa, Asia, New Zealand, and Australia. This study aims to determine the commercial status of natural dyes. Each continent has its own traditions and specific dyestuffs. The availability of natural dyes can vary depending on several aspects, including plant species, temperature, and harvesting techniques, which poses a challenge to the work of designers and crafters. While certain plants may only provide dyes during specific seasons, others may do so continuously. To find the ideal time to collect natural dyes, it is critical to research various plant species and their harvesting techniques. Furthermore, to guarantee the quality and colour of the dye, plant material must be handled and processed properly. This research was conducted via an internet search, and results were searched systematically for commercial stakeholders in the field. The research question looked at commercial players in the field of natural dyes. This qualitative case study interpreted the data using thematic analysis. Each webpage was screenshotted and analyzed in reflection on to research question. Online content analysis means systematically coding and analyzing qualitative data. The most evident result was that the natural dyes interest in different parts of the World. There are clothing collections dyed with natural dyes, dyestuff stores, and courses for natural dyeing. This article presents the designers who work with natural dyes and actors who are involved with the natural dye industry. Several websites emphasized the safety and environmental benefits of natural dyes. Many of them included eye-catching images of textiles dyed naturally, and the colours of such dyes are thought to be attractive since they are beautiful and natural hues. The search did not find big-scale industrial solutions for natural dyes, but there were several instances of dyeing with natural dyes. Understanding the players, designers, and stakeholders in the natural dye business is the purpose of this article. The comprehension of the current state of the art illustrates the direction that the natural dye business is currently taking.

Keywords: commercial solutions, environmental issues, key stakeholders, natural dyes, sustainability, textile dyeing

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21 Investigation of Processing Conditions on Rheological Features of Emulsion Gels and Oleogels Stabilized by Biopolymers

Authors: M. Sarraf, J. E. Moros, M. C. Sánchez

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Oleogels are self-standing systems that are able to trap edible liquid oil into a tridimensional network and also help to use less fat by forming crystallization oleogelators. There are different ways to generate oleogelation and oil structuring, including direct dispersion, structured biphasic systems, oil sorption, and indirect method (emulsion-template). The selection of processing conditions as well as the composition of the oleogels is essential to obtain a stable oleogel with characteristics suitable for its purpose. In this sense, one of the ingredients widely used in food products to produce oleogels and emulsions is polysaccharides. Basil seed gum (BSG), with the scientific name Ocimum basilicum, is a new native polysaccharide with high viscosity and pseudoplastic behavior because of its high molecular weight in the food industry. Also, proteins can stabilize oil in water due to the presence of amino and carboxyl moieties that result in surface activity. Whey proteins are widely used in the food industry due to available, cheap ingredients, nutritional and functional characteristics such as emulsifier and a gelling agent, thickening, and water-binding capacity. In general, the interaction of protein and polysaccharides has a significant effect on the food structures and their stability, like the texture of dairy products, by controlling the interactions in macromolecular systems. Using edible oleogels as oil structuring helps for targeted delivery of a component trapped in a structural network. Therefore, the development of efficient oleogel is essential in the food industry. A complete understanding of the important points, such as the ratio oil phase, processing conditions, and concentrations of biopolymers that affect the formation and stability of the emulsion, can result in crucial information in the production of a suitable oleogel. In this research, the effects of oil concentration and pressure used in the manufacture of the emulsion prior to obtaining the oleogel have been evaluated through the analysis of droplet size and rheological properties of obtained emulsions and oleogels. The results show that the emulsion prepared in the high-pressure homogenizer (HPH) at higher pressure values has smaller droplet sizes and a higher uniformity in the size distribution curve. On the other hand, in relation to the rheological characteristics of the emulsions and oleogels obtained, the predominantly elastic character of the systems must be noted, as they present values of the storage modulus higher than those of losses, also showing an important plateau zone, typical of structured systems. In the same way, if steady-state viscous flow tests have been analyzed on both emulsions and oleogels, the result is that, once again, the pressure used in the homogenizer is an important factor for obtaining emulsions with adequate droplet size and the subsequent oleogel. Thus, various routes for trapping oil inside a biopolymer matrix with adjustable mechanical properties could be applied for the creation of the three-dimensional network in order to the oil absorption and creating oleogel.

Keywords: basil seed gum, particle size, viscoelastic properties, whey protein

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20 Elements of Creativity and Innovation

Authors: Fadwa Al Bawardi

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In March 2021, the Saudi Arabian Council of Ministers issued a decision to form a committee called the "Higher Committee for Research, Development and Innovation," a committee linked to the Council of Economic and Development Affairs, chaired by the Chairman of the Council of Economic and Development Affairs, and concerned with the development of the research, development and innovation sector in the Kingdom. In order to talk about the dimensions of this wonderful step, let us first try to answer the following questions. Is there a difference between creativity and innovation..? What are the factors of creativity in the individual. Are they mental genetic factors or are they factors that an individual acquires through learning..? The methodology included surveys that have been conducted on more than 500 individuals, males and females, between the ages of 18 till 60. And the answer is. "Creativity" is the creation of a new idea, while "Innovation" is the development of an already existing idea in a new, successful way. They are two sides of the same coin, as the "creative idea" needs to be developed and transformed into an "innovation" in order to achieve either strategic achievements at the level of countries and institutions to enhance organizational intelligence, or achievements at the level of individuals. For example, the beginning of smart phones was just a creative idea from IBM in 1994, but the actual successful innovation for the manufacture, development and marketing of these phones was through Apple later. Nor does creativity have to be hereditary. There are three basic factors for creativity: The first factor is "the presence of a challenge or an obstacle" that the individual faces and seeks thinking to find solutions to overcome, even if thinking requires a long time. The second factor is the "environment surrounding" of the individual, which includes science, training, experience gained, the ability to use techniques, as well as the ability to assess whether the idea is feasible or otherwise. To achieve this factor, the individual must be aware of own skills, strengths, hobbies, and aspects in which one can be creative, and the individual must also be self-confident and courageous enough to suggest those new ideas. The third factor is "Experience and the Ability to Accept Risk and Lack of Initial Success," and then learn from mistakes and try again tirelessly. There are some tools and techniques that help the individual to reach creative and innovative ideas, such as: Mind Maps tool, through which the available information is drawn by writing a short word for each piece of information and arranging all other relevant information through clear lines, which helps in logical thinking and correct vision. There is also a tool called "Flow Charts", which are graphics that show the sequence of data and expected results according to an ordered scenario of events and workflow steps, giving clarity to the ideas, their sequence, and what is expected of them. There are also other great tools such as the Six Hats tool, a useful tool to be applied by a group of people for effective planning and detailed logical thinking, and the Snowball tool. And all of them are tools that greatly help in organizing and arranging mental thoughts, and making the right decisions. It is also easy to learn, apply and use all those tools and techniques to reach creative and innovative solutions. The detailed figures and results of the conducted surveys are available upon request, with charts showing the %s based on gender, age groups, and job categories.

Keywords: innovation, creativity, factors, tools

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19 Poly(Methyl Methacrylate) Degradation Products and Its in vitro Cytotoxicity Evaluation in NIH3T3 Cells

Authors: Lesly Y Carmona-Sarabia, Luisa Barraza-Vergara, Vilmalí López-Mejías, Wandaliz Torres-García, Maribella Domenech-Garcia, Madeline Torres-Lugo

Abstract:

Biosensors are used in many applications providing real-time monitoring to treat long-term conditions. Thus, understanding the physicochemical properties and biological side effects on the skin of polymers (e. g., poly(methyl methacrylate), PMMA) employed in the fabrication of wearable biosensors is crucial for the selection of manufacturing materials within this field. The PMMA (hydrophobic and thermoplastic polymer) is commonly employed as a coating material or substrate in the fabrication of wearable devices. The cytotoxicityof PMMA (including residual monomers or degradation products) on the skin, in terms of cells and tissue, is required to prevent possible adverse effects (cell death, skin reactions, sensitization) on human health. Within this work, accelerated aging of PMMA (Mw ~ 15000) through thermal and photochemical degradation was under-taken. The accelerated aging of PMMA was carried out by thermal (200°C, 1h) and photochemical degradation (UV-Vis, 8-15d) adapted employing ISO protocols (ISO-10993-12, ISO-4892-1:2016, ISO-877-1:2009, ISO-188: 2011). In addition, in vitro cytotoxicity evaluation of PMMA degradation products was performed using NIH3T3 fibroblast cells to assess the response of skin tissues (in terms of cell viability) exposed with polymers utilized to manufacture wearable biosensors, such as PMMA. The PMMA (Mw ~ 15000) before and after accelerated aging experiments was characterized by thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC), powder X-ray diffractogram (PXRD), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) to determine and verify the successful degradation of this polymer under the specific conditions previously mention. The degradation products were characterized through nuclear magnetic resonance (NMR) to identify possible byproducts generated after the accelerated aging. Results demonstrated a percentage (%) weight loss between 1.5-2.2% (TGA thermographs) for PMMA after accelerated aging. The EDS elemental analysis reveals a 1.32 wt.% loss of carbon for PMMA after thermal degradation. These results might be associated with the amount (%) of PMMA degrade after the accelerated aging experiments. Furthermore, from the thermal degradation products was detected the presence of the monomer and methyl formate (low concentrations) and a low molecular weight radical (·COOCH3) in higher concentrations by NMR. In the photodegradation products, methyl formate was detected in higher concentrations. These results agree with the proposed thermal or photochemical degradation mechanisms found in the literature.1,2 Finally, significant cytotoxicity on the NIH3T3 cells was obtained for the thermal and photochemical degradation products. A decrease in cell viability by > 90% (stock solutions) was observed. It is proposed that the presence of byproducts (e.g. methyl formate or radicals such as ·COOCH₃) from the PMMA degradation might be responsible for the cytotoxicity observed in the NIH3T3 fibroblast cells. Additionally, experiments using skin models will be employed to compare with the NIH3T3 fibroblast cells model.

Keywords: biosensors, polymer, skin irritation, degradation products, cell viability

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18 Magnetic Carriers of Organic Selenium (IV) Compounds: Physicochemical Properties and Possible Applications in Anticancer Therapy

Authors: E. Mosiniewicz-Szablewska, P. Suchocki, P. C. Morais

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Despite the significant progress in cancer treatment, there is a need to search for new therapeutic methods in order to minimize side effects. Chemotherapy, the main current method of treating cancer, is non-selective and has a number of limitations. Toxicity to healthy cells is undoubtedly the biggest problem limiting the use of many anticancer drugs. The problem of how to kill cancer without harming a patient can be solved by using organic selenium (IV) compounds. Organic selenium (IV) compounds are a new class of materials showing a strong anticancer activity. They are first organic compounds containing selenium at the +4 oxidation level and therefore they eliminate the multidrug-resistance for all tumor cell lines tested so far. These materials are capable of selectively killing cancer cells without damaging the healthy ones. They are obtained by the incorporation of selenous acid (H2SeO3) into molecules of fatty acids of sunflower oil and therefore, they are inexpensive to manufacture. Attaching these compounds to magnetic carriers enables their precise delivery directly to the tumor area and the simultaneous application of the magnetic hyperthermia, thus creating a huge opportunity to effectively get rid of the tumor without any side effects. Polylactic-co-glicolic acid (PLGA) nanocapsules loaded with maghemite (-Fe2O3) nanoparticles and organic selenium (IV) compounds are successfully prepared by nanoprecipitation method. In vitro antitumor activity of the nanocapsules were evidenced using murine melanoma (B16-F10), oral squamos carcinoma (OSCC) and murine (4T1) and human (MCF-7) breast lines. Further exposure of these cells to an alternating magnetic field increased the antitumor effect of nanocapsules. Moreover, the nanocapsules presented antitumor effect while not affecting normal cells. Magnetic properties of the nanocapsules were investigated by means of dc magnetization, ac susceptibility and electron spin resonance (ESR) measurements. The nanocapsules presented a typical superparamagnetic behavior around room temperature manifested itself by the split between zero field-cooled/field-cooled (ZFC/FC) magnetization curves and the absence of hysteresis on the field-dependent magnetization curve above the blocking temperature. Moreover, the blocking temperature decreased with increasing applied magnetic field. The superparamagnetic character of the nanocapsules was also confirmed by the occurrence of a maximum in temperature dependences of both real ′(T) and imaginary ′′ (T) components of the ac magnetic susceptibility, which shifted towards higher temperatures with increasing frequency. Additionally, upon decreasing the temperature the ESR signal shifted to lower fields and gradually broadened following closely the predictions for the ESR of superparamagnetoc nanoparticles. The observed superparamagnetic properties of nanocapsules enable their simple manipulation by means of magnetic field gradient, after introduction into the blood stream, which is a necessary condition for their use as magnetic drug carriers. The observed anticancer and superparamgnetic properties show that the magnetic nanocapsules loaded with organic selenium (IV) compounds should be considered as an effective material system for magnetic drug delivery and magnetohyperthermia inductor in antitumor therapy.

Keywords: cancer treatment, magnetic drug delivery system, nanomaterials, nanotechnology

Procedia PDF Downloads 175