Search results for: homogeneous combustion
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 1216

Search results for: homogeneous combustion

46 Arc Plasma Application for Solid Waste Processing

Authors: Vladimir Messerle, Alfred Mosse, Alexandr Ustimenko, Oleg Lavrichshev

Abstract:

Hygiene and sanitary study of typical medical-biological waste made in Kazakhstan, Russia, Belarus and other countries show that their risk to the environment is much higher than that of most chemical wastes. For example, toxicity of solid waste (SW) containing cytotoxic drugs and antibiotics is comparable to toxicity of radioactive waste of high and medium level activity. This report presents the results of the thermodynamic analysis of thermal processing of SW and experiments at the developed plasma unit for SW processing. Thermodynamic calculations showed that the maximum yield of the synthesis gas at plasma gasification of SW in air and steam mediums is achieved at a temperature of 1600K. At the air plasma gasification of SW high-calorific synthesis gas with a concentration of 82.4% (СO – 31.7%, H2 – 50.7%) can be obtained, and at the steam plasma gasification – with a concentration of 94.5% (СO – 33.6%, H2 – 60.9%). Specific heat of combustion of the synthesis gas produced by air gasification amounts to 14267 kJ/kg, while by steam gasification - 19414 kJ/kg. At the optimal temperature (1600 K), the specific power consumption for air gasification of SW constitutes 1.92 kWh/kg, while for steam gasification - 2.44 kWh/kg. Experimental study was carried out in a plasma reactor. This is device of periodic action. The arc plasma torch of 70 kW electric power is used for SW processing. Consumption of SW was 30 kg/h. Flow of plasma-forming air was 12 kg/h. Under the influence of air plasma flame weight average temperature in the chamber reaches 1800 K. Gaseous products are taken out of the reactor into the flue gas cooling unit, and the condensed products accumulate in the slag formation zone. The cooled gaseous products enter the gas purification unit, after which via gas sampling system is supplied to the analyzer. Ventilation system provides a negative pressure in the reactor up to 10 mm of water column. Condensed products of SW processing are removed from the reactor after its stopping. By the results of experiments on SW plasma gasification the reactor operating conditions were determined, the exhaust gas analysis was performed and the residual carbon content in the slag was determined. Gas analysis showed the following composition of the gas at the exit of gas purification unit, (vol.%): СO – 26.5, H2 – 44.6, N2–28.9. The total concentration of the syngas was 71.1%, which agreed well with the thermodynamic calculations. The discrepancy between experiment and calculation by the yield of the target syngas did not exceed 16%. Specific power consumption for SW gasification in the plasma reactor according to the results of experiments amounted to 2.25 kWh/kg of working substance. No harmful impurities were found in both gas and condensed products of SW plasma gasification. Comparison of experimental results and calculations showed good agreement. Acknowledgement—This work was supported by Ministry of Education and Science of the Republic of Kazakhstan and Ministry of Education and Science of the Russian Federation (Agreement on grant No. 14.607.21.0118, project RFMEF160715X0118).

Keywords: coal, efficiency, ignition, numerical modeling, plasma-fuel system, plasma generator

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45 Synthesis of Belite Cements at Low Temperature from Silica Fume and Natural Commercial Zeolite

Authors: Tatiana L. Avalos-Rendon, Elias A. Pasten Chelala, Carlos J. Mendoza EScobedo, Ignacio A. Figueroa, Victor H. Lara, Luis M. Palacios-Romero

Abstract:

The cement industry is facing cost increments in energy supply, requirements for reduction of CO₂, and insufficient supply of raw materials of good quality. According to all these environmental issues, cement industry must change its consumption patterns and reduce CO₂ emissions to the atmosphere. This can be achieved by generating environmental consciousness, which encourages the use of industrial by-products and/or recycling for the production of cement, as well as alternate, environment-friendly methods of synthesis which reduce CO₂. Calcination is the conventional method for the obtainment of Portland cement clinker. This method consists of grinding and mixing of raw materials (limestone, clay, etc.) in an adequate dosage. Resulting mix has a clinkerization temperature of 1450 °C so that the formation of the main component occur: alite (Ca₃SiO₅, C₃S). Considering that the energy required to produce C₃S is 1810 kJ kg -1, calcination method for the obtainment of clinker represents two major disadvantages: long thermal treatment and elevated temperatures of synthesis, both of which cause high emissions of carbon dioxide (CO₂) to the atmosphere. Belite Portland clinker is characterized by having a low content of calcium oxide (CaO), causing the presence of alite to diminish and favoring the formation of belite (β-Ca₂SiO₄, C₂S), so production of clinker requires a reduced energy consumption (1350 kJ kg-1), releasing less CO₂ to the atmosphere. Conventionally, β-Ca₂SiO₄ is synthetized by the calcination of calcium carbonate (CaCO₃) and silicon dioxide (SiO₂) through the reaction in solid state at temperatures greater than 1300 °C. Resulting belite shows low hydraulic reactivity. Therefore, this study concerns a new simple modified combustion method for the synthesis of two belite cements at low temperatures (1000 °C). Silica fume, as subproduct of metallurgic industry and commercial natural zeolite were utilized as raw materials. These are considered low-cost materials and were utilized with no additional purification process. Belite cements properties were characterized by XRD, SEM, EDS and BET techniques. Hydration capacity of belite cements was calculated while the mechanical strength was determined in ordinary Portland cement specimens (PC) with a 10% partial replacement of the belite cements obtained. Results showed belite cements presented relatively high surface áreas, at early ages mechanical strengths similar to those of alite cement and comparable to strengths of belite cements obtained by different synthesis methods. Cements obtained in this work present good hydraulic reactivity properties.

Keywords: belite, silica fume, zeolite, hydraulic reactivity

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44 Superparamagnetic Core Shell Catalysts for the Environmental Production of Fuels from Renewable Lignin

Authors: Cristina Opris, Bogdan Cojocaru, Madalina Tudorache, Simona M. Coman, Vasile I. Parvulescu, Camelia Bala, Bahir Duraki, Jeroen A. Van Bokhoven

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The tremendous achievements in the development of the society concretized by more sophisticated materials and systems are merely based on non-renewable resources. Consequently, after more than two centuries of intensive development, among others, we are faced with the decrease of the fossil fuel reserves, an increased impact of the greenhouse gases on the environment, and economic effects caused by the fluctuations in oil and mineral resource prices. The use of biomass may solve part of these problems, and recent analyses demonstrated that from the perspective of the reduction of the emissions of carbon dioxide, its valorization may bring important advantages conditioned by the usage of genetic modified fast growing trees or wastes, as primary sources. In this context, the abundance and complex structure of lignin may offer various possibilities of exploitation. However, its transformation in fuels or chemicals supposes a complex chemistry involving the cleavage of C-O and C-C bonds and altering of the functional groups. Chemistry offered various solutions in this sense. However, despite the intense work, there are still many drawbacks limiting the industrial application. Thus, the proposed technologies considered mainly homogeneous catalysts meaning expensive noble metals based systems that are hard to be recovered at the end of the reaction. Also, the reactions were carried out in organic solvents that are not acceptable today from the environmental point of view. To avoid these problems, the concept of this work was to investigate the synthesis of superparamagnetic core shell catalysts for the fragmentation of lignin directly in the aqueous phase. The magnetic nanoparticles were covered with a nanoshell of an oxide (niobia) with a double role: to protect the magnetic nanoparticles and to generate a proper (acidic) catalytic function and, on this composite, cobalt nanoparticles were deposed in order to catalyze the C-C bond splitting. With this purpose, we developed a protocol to prepare multifunctional and magnetic separable nano-composite Co@Nb2O5@Fe3O4 catalysts. We have also established an analytic protocol for the identification and quantification of the fragments resulted from lignin depolymerization in both liquid and solid phase. The fragmentation of various lignins occurred on the prepared materials in high yields and with very good selectivity in the desired fragments. The optimization of the catalyst composition indicated a cobalt loading of 4wt% as optimal. Working at 180 oC and 10 atm H2 this catalyst allowed a conversion of lignin up to 60% leading to a mixture containing over 96% in C20-C28 and C29-C37 fragments that were then completely fragmented to C12-C16 in a second stage. The investigated catalysts were completely recyclable, and no leaching of the elements included in the composition was determined by inductively coupled plasma optical emission spectrometry (ICP-OES).

Keywords: superparamagnetic core-shell catalysts, environmental production of fuels, renewable lignin, recyclable catalysts

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43 Numerical Model of Crude Glycerol Autothermal Reforming to Hydrogen-Rich Syngas

Authors: A. Odoom, A. Salama, H. Ibrahim

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Hydrogen is a clean source of energy for power production and transportation. The main source of hydrogen in this research is biodiesel. Glycerol also called glycerine is a by-product of biodiesel production by transesterification of vegetable oils and methanol. This is a reliable and environmentally-friendly source of hydrogen production than fossil fuels. A typical composition of crude glycerol comprises of glycerol, water, organic and inorganic salts, soap, methanol and small amounts of glycerides. Crude glycerol has limited industrial application due to its low purity thus, the usage of crude glycerol can significantly enhance the sustainability and production of biodiesel. Reforming techniques is an approach for hydrogen production mainly Steam Reforming (SR), Autothermal Reforming (ATR) and Partial Oxidation Reforming (POR). SR produces high hydrogen conversions and yield but is highly endothermic whereas POR is exothermic. On the downside, PO yields lower hydrogen as well as large amount of side reactions. ATR which is a fusion of partial oxidation reforming and steam reforming is thermally neutral because net reactor heat duty is zero. It has relatively high hydrogen yield, selectivity as well as limits coke formation. The complex chemical processes that take place during the production phases makes it relatively difficult to construct a reliable and robust numerical model. Numerical model is a tool to mimic reality and provide insight into the influence of the parameters. In this work, we introduce a finite volume numerical study for an 'in-house' lab-scale experiment of ATR. Previous numerical studies on this process have considered either using Comsol or nodal finite difference analysis. Since Comsol is a commercial package which is not readily available everywhere and lab-scale experiment can be considered well mixed in the radial direction. One spatial dimension suffices to capture the essential feature of ATR, in this work, we consider developing our own numerical approach using MATLAB. A continuum fixed bed reactor is modelled using MATLAB with both pseudo homogeneous and heterogeneous models. The drawback of nodal finite difference formulation is that it is not locally conservative which means that materials and momenta can be generated inside the domain as an artifact of the discretization. Control volume, on the other hand, is locally conservative and suites very well problems where materials are generated and consumed inside the domain. In this work, species mass balance, Darcy’s equation and energy equations are solved using operator splitting technique. Therefore, diffusion-like terms are discretized implicitly while advection-like terms are discretized explicitly. An upwind scheme is adapted for the advection term to ensure accuracy and positivity. Comparisons with the experimental data show very good agreements which build confidence in our modeling approach. The models obtained were validated and optimized for better results.

Keywords: autothermal reforming, crude glycerol, hydrogen, numerical model

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42 Experimental Investigation of Absorbent Regeneration Techniques to Lower the Cost of Combined CO₂ and SO₂ Capture Process

Authors: Bharti Garg, Ashleigh Cousins, Pauline Pearson, Vincent Verheyen, Paul Feron

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The presence of SO₂ in power plant flue gases makes flue gas desulfurization (FGD) an essential requirement prior to post combustion CO₂ (PCC) removal facilities. Although most of the power plants worldwide deploy FGD in order to comply with environmental regulations, generally the achieved SO₂ levels are not sufficiently low for the flue gases to enter the PCC unit. The SO₂ level in the flue gases needs to be less than 10 ppm to effectively operate the PCC installation. The existing FGD units alone cannot bring down the SO₂ levels to or below 10 ppm as required for CO₂ capture. It might require an additional scrubber along with the existing FGD unit to bring the SO₂ to the desired levels. The absence of FGD units in Australian power plants brings an additional challenge. SO₂ concentrations in Australian power station flue gas emissions are in the range of 100-600 ppm. This imposes a serious barrier on the implementation of standard PCC technologies in Australia. CSIRO’s developed CS-Cap process is a unique solution to capture SO₂ and CO₂ in a single column with single absorbent which can potentially bring cost-effectiveness to the commercial deployment of carbon capture in Australia, by removing the need for FGD. Estimated savings of removing SO₂ through a similar process as CS-Cap is around 200 MMUSD for a 500 MW Australian power plant. Pilot plant trials conducted to generate the proof of concept resulted in 100% removal of SO₂ from flue gas without utilising standard limestone-based FGD. In this work, removal of absorbed sulfur from aqueous amine absorbents generated in the pilot plant trials has been investigated by reactive crystallisation and thermal reclamation. More than 95% of the aqueous amines can be reclaimed back from the sulfur loaded absorbent via reactive crystallisation. However, the recovery of amines through thermal reclamation is limited and depends on the sulfur loading on the spent absorbent. The initial experimental work revealed that reactive crystallisation is a better fit for CS-Cap’s sulfur-rich absorbent especially when it is also capable of generating K₂SO₄ crystals of highly saleable quality ~ 99%. Initial cost estimation carried on both the technologies resulted in almost similar capital expenditure; however, the operating cost is considerably higher in thermal reclaimer than that in crystalliser. The experimental data generated in the laboratory from both the regeneration techniques have been used to generate the simulation model in Aspen Plus. The simulation model illustrates the economic benefits which could be gained by removing flue gas desulfurization prior to standard PCC unit and replacing it with a CS-Cap absorber column co-capturing CO₂ and SO₂, and it's absorbent regeneration system which would be either reactive crystallisation or thermal reclamation.

Keywords: combined capture, cost analysis, crystallisation, CS-Cap, flue gas desulfurisation, regeneration, sulfur, thermal reclamation

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41 Evaluation of the Boiling Liquid Expanding Vapor Explosion Thermal Effects in Hassi R'Mel Gas Processing Plant Using Fire Dynamics Simulator

Authors: Brady Manescau, Ilyas Sellami, Khaled Chetehouna, Charles De Izarra, Rachid Nait-Said, Fati Zidani

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During a fire in an oil and gas refinery, several thermal accidents can occur and cause serious damage to people and environment. Among these accidents, the BLEVE (Boiling Liquid Expanding Vapor Explosion) is most observed and remains a major concern for risk decision-makers. It corresponds to a violent vaporization of explosive nature following the rupture of a vessel containing a liquid at a temperature significantly higher than its normal boiling point at atmospheric pressure. Their effects on the environment generally appear in three ways: blast overpressure, radiation from the fireball if the liquid involved is flammable and fragment hazards. In order to estimate the potential damage that would be caused by such an explosion, risk decision-makers often use quantitative risk analysis (QRA). This analysis is a rigorous and advanced approach that requires a reliable data in order to obtain a good estimate and control of risks. However, in most cases, the data used in QRA are obtained from the empirical correlations. These empirical correlations generally overestimate BLEVE effects because they are based on simplifications and do not take into account real parameters like the geometry effect. Considering that these risk analyses are based on an assessment of BLEVE effects on human life and plant equipment, more precise and reliable data should be provided. From this point of view, the CFD modeling of BLEVE effects appears as a solution to the empirical law limitations. In this context, the main objective is to develop a numerical tool in order to predict BLEVE thermal effects using the CFD code FDS version 6. Simulations are carried out with a mesh size of 1 m. The fireball source is modeled as a vertical release of hot fuel in a short time. The modeling of fireball dynamics is based on a single step combustion using an EDC model coupled with the default LES turbulence model. Fireball characteristics (diameter, height, heat flux and lifetime) issued from the large scale BAM experiment are used to demonstrate the ability of FDS to simulate the various steps of the BLEVE phenomenon from ignition up to total burnout. The influence of release parameters such as the injection rate and the radiative fraction on the fireball heat flux is also presented. Predictions are very encouraging and show good agreement in comparison with BAM experiment data. In addition, a numerical study is carried out on an operational propane accumulator in an Algerian gas processing plant of SONATRACH company located in the Hassi R’Mel Gas Field (the largest gas field in Algeria).

Keywords: BLEVE effects, CFD, FDS, fireball, LES, QRA

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40 The Effectiveness of Multi-Media Experiential Training Programme on Advance Care Planning in Enhancing Acute Care Nurses’ Knowledge and Confidence in Advance Care Planning Discussion: An Interim Report

Authors: Carmen W. H. Chan, Helen Y. L. Chan, Kai Chow Choi, Ka Ming Chow, Cecilia W. M. Kwan, Nancy H. Y. Ng, Jackie Robinson

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Introduction: In Hong Kong, a significant number of deaths occur in acute care wards, which requires nurses in these settings to provide end-of-life care and lead ACP implementation. However, nurses in these settings, in fact, have very low-level involvement in ACP discussions because of limited training in ACP conversations. Objective: This study aims to assess the impact of a multi-media experiential ACP (MEACP) training program, which is guided by the experiential learning model and theory of planned behaviour, on nurses' knowledge and confidence in assisting patients with ACP. Methodology: The study utilizes a cluster randomized controlled trial with a 12-week follow-up. Eligible nurses working in acute care hospital wards are randomly assigned at the ward level, in a 1:1 ratio, to either the control group (no ACP education) or the intervention group (4-week MEACP training program). The training programme includes training through a webpage and mobile application, as well as a face-to-face training workshop with enhanced lectures and role play, which is based on the Theory of Planned Behavior and Kolb's Experiential Learning Model. Questionnaires were distributed to assess nurses' knowledge (a 10-item true/false questionnaire) and level of confidence (five-point Likert scale) in ACP at baseline (T0), four weeks after the baseline assessment (T1), and 12 weeks after T1 (T2). In this interim report, data analysis was mainly descriptive in nature. Result: The interim report focuses on the preliminary results of 165 nurses at T0 (Control: 74, Intervention: 91) over a 5-month period, 69 nurses from the control group who completed the 4-week follow-up and 65 nurses from the intervention group who completed the 4-week MEACP training program at T1. The preliminary attrition rate is 6.8% and 28.6% for the control and intervention groups, respectively, as some nurses did not complete the whole set of online modules. At baseline, the two groups were generally homogeneous in terms of their years of nursing practice, weekly working hours, working title, and level of education, as well as ACP knowledge and confidence levels. The proportion of nurses who answered all ten knowledge questions correctly increased from 13.8% (T0) to 66.2% (T1) for the intervention group and from 13% (T0) to 20.3% (T1) for the control group. The nurses in the intervention group answered an average of 7.57 and 9.43 questions correctly at T0 and T1, respectively. They showed a greater improvement in the knowledge assessment at T1 with respect to T0 when compared with their counterparts in the control group (mean difference of change score, Δ=1.22). They also exhibited a greater gain in level of confidence at T1 compared to their colleagues in the control group (Δ=0.91). T2 data is yet available. Conclusion: The prevalence of nurses engaging in ACP and their level of knowledge about ACP in Hong Kong is low. The MEACP training program can enrich nurses by providing them with more knowledge about ACP and increasing their confidence in conducting ACP.

Keywords: advance directive, advance care planning, confidence, knowledge, multi-media experiential, randomised control trial

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39 Physiological Effects on Scientist Astronaut Candidates: Hypobaric Training Assessment

Authors: Pedro Llanos, Diego García

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This paper is addressed to expanding our understanding of the effects of hypoxia training on our bodies to better model its dynamics and leverage some of its implications and effects on human health. Hypoxia training is a recommended practice for military and civilian pilots that allow them to recognize their early hypoxia signs and symptoms, and Scientist Astronaut Candidates (SACs) who underwent hypobaric hypoxia (HH) exposure as part of a training activity for prospective suborbital flight applications. This observational-analytical study describes physiologic responses and symptoms experienced by a SAC group before, during and after HH exposure and proposes a model for assessing predicted versus observed physiological responses. A group of individuals with diverse Science Technology Engineering Mathematics (STEM) backgrounds conducted a hypobaric training session to an altitude up to 22,000 ft (FL220) or 6,705 meters, where heart rate (HR), breathing rate (BR) and core temperature (Tc) were monitored with the use of a chest strap sensor pre and post HH exposure. A pulse oximeter registered levels of saturation of oxygen (SpO2), number and duration of desaturations during the HH chamber flight. Hypoxia symptoms as described by the SACs during the HH training session were also registered. This data allowed to generate a preliminary predictive model of the oxygen desaturation and O2 pressure curve for each subject, which consists of a sixth-order polynomial fit during exposure, and a fifth or fourth-order polynomial fit during recovery. Data analysis showed that HR and BR showed no significant differences between pre and post HH exposure in most of the SACs, while Tc measures showed slight but consistent decrement changes. All subjects registered SpO2 greater than 94% for the majority of their individual HH exposures, but all of them presented at least one clinically significant desaturation (SpO2 < 85% for more than 5 seconds) and half of the individuals showed SpO2 below 87% for at least 30% of their HH exposure time. Finally, real time collection of HH symptoms presented temperature somatosensory perceptions (SP) for 65% of individuals, and task-focus issues for 52.5% of individuals as the most common HH indications. 95% of the subjects experienced HH onset symptoms below FL180; all participants achieved full recovery of HH symptoms within 1 minute of donning their O2 mask. The current HH study performed on this group of individuals suggests a rapid and fully reversible physiologic response after HH exposure as expected and obtained in previous studies. Our data showed consistent results between predicted versus observed SpO2 curves during HH suggesting a mathematical function that may be used to model HH performance deficiencies. During the HH study, real-time HH symptoms were registered providing evidenced SP and task focusing as the earliest and most common indicators. Finally, an assessment of HH signs of symptoms in a group of heterogeneous, non-pilot individuals showed similar results to previous studies in homogeneous populations of pilots.

Keywords: slow onset hypoxia, hypobaric chamber training, altitude sickness, symptoms and altitude, pressure cabin

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38 Vibration and Freeze-Thaw Cycling Tests on Fuel Cells for Automotive Applications

Authors: Gema M. Rodado, Jose M. Olavarrieta

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Hydrogen fuel cell technologies have experienced a great boost in the last decades, significantly increasing the production of these devices for both stationary and portable (mainly automotive) applications; these are influenced by two main factors: environmental pollution and energy shortage. A fuel cell is an electrochemical device that converts chemical energy directly into electricity by using hydrogen and oxygen gases as reactive components and obtaining water and heat as byproducts of the chemical reaction. Fuel cells, specifically those of Proton Exchange Membrane (PEM) technology, are considered an alternative to internal combustion engines, mainly because of the low emissions they produce (almost zero), high efficiency and low operating temperatures (< 373 K). The introduction and use of fuel cells in the automotive market requires the development of standardized and validated procedures to test and evaluate their performance in different environmental conditions including vibrations and freeze-thaw cycles. These situations of vibration and extremely low/high temperatures can affect the physical integrity or even the excellent operation or performance of the fuel cell stack placed in a vehicle in circulation or in different climatic conditions. The main objective of this work is the development and validation of vibration and freeze-thaw cycling test procedures for fuel cell stacks that can be used in a vehicle in order to consolidate their safety, performance, and durability. In this context, different experimental tests were carried out at the facilities of the National Hydrogen Centre (CNH2). The experimental equipment used was: A vibration platform (shaker) for vibration test analysis on fuel cells in three axes directions with different vibration profiles. A walk-in climatic chamber to test the starting, operating, and stopping behavior of fuel cells under defined extreme conditions. A test station designed and developed by the CNH2 to test and characterize PEM fuel cell stacks up to 10 kWe. A 5 kWe PEM fuel cell stack in off-operation mode was used to carry out two independent experimental procedures. On the one hand, the fuel cell was subjected to a sinusoidal vibration test on the shaker in the three axes directions. It was defined by acceleration and amplitudes in the frequency range of 7 to 200 Hz for a total of three hours in each direction. On the other hand, the climatic chamber was used to simulate freeze-thaw cycles by defining a temperature range between +313 K and -243 K with an average relative humidity of 50% and a recommended ramp up and rump down of 1 K/min. The polarization curve and gas leakage rate were determined before and after the vibration and freeze-thaw tests at the fuel cell stack test station to evaluate the robustness of the stack. The results were very similar, which indicates that the tests did not affect the fuel cell stack structure and performance. The proposed procedures were verified and can be used as an initial point to perform other tests with different fuel cells.

Keywords: climatic chamber, freeze-thaw cycles, PEM fuel cell, shaker, vibration tests

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37 Surface Adjustments for Endothelialization of Decellularized Porcine Pericardium

Authors: M. Markova, E. Filova, O. Kaplan, R. Matejka, L. Bacakova

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The porcine pericardium is used as a material for cardiac and aortic valves substitutes. Current biological aortic heart valve prosthesis have a limited lifetime period because they undergo degeneration. In order to make them more biocompatible and prolong their lifetime it is necessary to reseed the decellularized prostheses with endothelial cells and with valve interstitial cells. The endothelialization of the prosthesis-surface may be supported by suitable chemical surface modification of the prosthesis. The aim of this study is to prepare bioactive fibrin layers which would both support endothelialization of porcine pericardium and enhance differentiation and maturation of the endothelial cells seeded. As a material for surface adjustments we used layers of fibrin with/without heparin and some of them with adsorbed or chemically bound FGF2, VEGF or their combination. Fibrin assemblies were prepared in 24-well cell culture plate and were seeded with HSVEC (Human Saphenous Vein Endothelial Cells) at a density of 20,000 cells per well in EGM-2 medium with 0.5% FS and without heparin, without FGF2 and without VEGF; medium was supplemented with aprotinin (200 U/mL). As a control, surface polystyrene (PS) was used. Fibrin was also used as homogeneous impregnation of the decellularized porcine pericardium throughout the scaffolds. Morphology, density, and viability of the seeded endothelial cells were observed from micrographs after staining the samples by LIVE/DEAD cytotoxicity/viability assay kit on the days 1, 3, and 7. Endothelial cells were immunocytochemically stained for proteins involved in cell adhesion, i.e. alphaV integrin, vinculin, and VE-cadherin, markers of endothelial cells differentiation and maturation, i.e. von Willebrand factor and CD31, and for extracellular matrix proteins typically produced by endothelial cells, i.e. type IV collagen and laminin. The staining intensities were subsequently quantified using a software. HSVEC cells grew on each of the prepared surfaces better than on control surface. They reached confluency. The highest cell densities were obtained on the surface of fibrin with heparin and both grow factors used together. Intensity of alphaV integrins staining was highest on samples with remained fibrin layer, i.e. on layers with lower cell densities, i.e. on fibrin without heparin. Vinculin staining was apparent, but was rather diffuse, on fibrin with both FGF2 and VEGF and on control PS. Endothelial cells on all samples were positively stained for von Willebrand factor and CD31. VE-cadherin receptors clusters were best developed on fibrin with heparin and growth factors. Significantly stronger staining of type IV collagen was observed on fibrin with heparin and both growth factors. Endothelial cells on all samples produced laminin-1. Decellularized pericardium was homogeneously filled with fibrin structures. These fibrin-modified pericardium samples will be further seeded with cells and cultured in a bioreactor. Fibrin layers with/without heparin and with adsorbed or chemically bound FGF2, VEGF or their combination are good surfaces for endothelialization of cardiovascular prostheses or porcine pericardium based heart valves. Supported by the Ministry of Health, grants No15-29153A and 15-32497A, and the Grant Agency of the Czech Republic, project No. P108/12/G108.

Keywords: aortic valves prosthesis, FGF2, heparin, HSVEC cells, VEGF

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36 A New Model to Perform Preliminary Evaluations of Complex Systems for the Production of Energy for Buildings: Case Study

Authors: Roberto de Lieto Vollaro, Emanuele de Lieto Vollaro, Gianluca Coltrinari

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The building sector is responsible, in many industrialized countries, for about 40% of the total energy requirements, so it seems necessary to devote some efforts in this area in order to achieve a significant reduction of energy consumption and of greenhouse gases emissions. The paper presents a study aiming at providing a design methodology able to identify the best configuration of the system building/plant, from a technical, economic and environmentally point of view. Normally, the classical approach involves a building's energy loads analysis under steady state conditions, and subsequent selection of measures aimed at improving the energy performance, based on previous experience made by architects and engineers in the design team. Instead, the proposed approach uses a sequence of two well known scientifically validated calculation methods (TRNSYS and RETScreen), that allow quite a detailed feasibility analysis. To assess the validity of the calculation model, an existing, historical building in Central Italy, that will be the object of restoration and preservative redevelopment, was selected as a case-study. The building is made of a basement and three floors, with a total floor area of about 3,000 square meters. The first step has been the determination of the heating and cooling energy loads of the building in a dynamic regime by means of TRNSYS, which allows to simulate the real energy needs of the building in function of its use. Traditional methodologies, based as they are on steady-state conditions, cannot faithfully reproduce the effects of varying climatic conditions and of inertial properties of the structure. With TRNSYS it is possible to obtain quite accurate and reliable results, that allow to identify effective combinations building-HVAC system. The second step has consisted of using output data obtained with TRNSYS as input to the calculation model RETScreen, which enables to compare different system configurations from the energy, environmental and financial point of view, with an analysis of investment, and operation and maintenance costs, so allowing to determine the economic benefit of possible interventions. The classical methodology often leads to the choice of conventional plant systems, while RETScreen provides a financial-economic assessment for innovative energy systems and low environmental impact. Computational analysis can help in the design phase, particularly in the case of complex structures with centralized plant systems, by comparing the data returned by the calculation model RETScreen for different design options. For example, the analysis performed on the building, taken as a case study, found that the most suitable plant solution, taking into account technical, economic and environmental aspects, is the one based on a CCHP system (Combined Cooling, Heating, and Power) using an internal combustion engine.

Keywords: energy, system, building, cooling, electrical

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35 Comparison of a Capacitive Sensor Functionalized with Natural or Synthetic Receptors Selective towards Benzo(a)Pyrene

Authors: Natalia V. Beloglazova, Pieterjan Lenain, Martin Hedstrom, Dietmar Knopp, Sarah De Saeger

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In recent years polycyclic aromatic hydrocarbons (PAHs), which represent a hazard to humans and entire ecosystem, have been receiving an increased interest due to their mutagenic, carcinogenic and endocrine disrupting properties. They are formed in all incomplete combustion processes of organic matter and, as a consequence, ubiquitous in the environment. Benzo(a)pyrene (BaP) is on the priority list published by the Environmental Agency (US EPA) as the first PAH to be identified as a carcinogen and has often been used as a marker for PAHs contamination in general. It can be found in different types of water samples, therefore, the European Commission set up a limit value of 10 ng L–1 (10 ppt) for BAP in water intended for human consumption. Generally, different chromatographic techniques are used for PAHs determination, but these assays require pre-concentration of analyte, create large amounts of solvent waste, and are relatively time consuming and difficult to perform on-site. An alternative robust, stand-alone, and preferably cheap solution is needed. For example, a sensing unit which can be submerged in a river to monitor and continuously sample BaP. An affinity sensor based on capacitive transduction was developed. Natural antibodies or their synthetic analogues can be used as ligands. Ideally the sensor should operate independently over a longer period of time, e.g. several weeks or months, therefore the use of molecularly imprinted polymers (MIPs) was discussed. MIPs are synthetic antibodies which are selective for a chosen target molecule. Their robustness allows application in environments for which biological recognition elements are unsuitable or denature. They can be reused multiple times, which is essential to meet the stand-alone requirement. BaP is a highly lipophilic compound and does not contain any functional groups in its structure, thus excluding non-covalent imprinting methods based on ionic interactions. Instead, the MIPs syntheses were based on non-covalent hydrophobic and π-π interactions. Different polymerization strategies were compared and the best results were demonstrated by the MIPs produced using electropolymerization. 4-vinylpyridin (VP) and divinylbenzene (DVB) were used as monomer and cross-linker in the polymerization reaction. The selectivity and recovery of the MIP were compared to a non-imprinted polymer (NIP). Electrodes were functionalized with natural receptor (monoclonal anti-BaP antibody) and with MIPs selective towards BaP. Different sets of electrodes were evaluated and their properties such as sensitivity, selectivity and linear range were determined and compared. It was found that both receptor can reach the cut-off level comparable to the established ML, and despite the fact that the antibody showed the better cross-reactivity and affinity, MIPs were more convenient receptor due to their ability to regenerate and stability in river till 7 days.

Keywords: antibody, benzo(a)pyrene, capacitive sensor, MIPs, river water

Procedia PDF Downloads 283
34 Presence, Distribution and Form of Calcium Oxalate Crystals in Relation to Age of Actinidia Deliciosa Leaves and Petioles

Authors: Muccifora S., Rinallo C., Bellani L.

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Calcium (Ca²+) is an element essential to the plant being involved in plant growth and development. At high concentrations, it is toxic and can influence every stage, process and cellular activity of plant life. Given its toxicity, cells implement mechanisms to compartmentalize calcium in a vacuole, endoplasmic reticulum, mitochondria, plastids and cell wall. One of the most effective mechanisms to reduce the excess of calcium, thus avoiding cellular damage, is its complexation with oxalic acid to form calcium oxalate crystals that are no longer osmotically or physiologically active. However, the sequestered calcium can be mobilized when the plant needs it. Calcium crystals can be accumulated in the vacuole of specialized sink-cells called idioblasts, with different crystalline forms (druse, raphyde and styloid) of diverse physiological meanings. Actinidia deliciosa cv. Hayward presents raphydes and styloid localized in idioblasts in cells of photosynthetic and non-photosynthetic tissues. The purpose of this work was to understand if there is a relationship between the age of Actinidia leaves and the presence, distribution, dimension and shape of oxalate crystals by means of light, fluorescent, polarized and transmission electron microscopy. Three vines from female plants were chosen at the beginning of the season and used throughout the study. The leaves with petioles were collected at various stages of development from the bottom to the shoot of the plants monthly from April to July. The samples were taken in corresponding areas of the central and lateral parts of the leaves and of the basal portion of the petiole. The results showed that in the leaves, the number of raphyde idioblasts decreased with the progress of the growing season, while the styloid idioblasts increased progressively, becoming very numerous in the upper nodes of July. In June and in July samples, in the vacuoles of the highest nodes, a portion regular in shape strongly stained with rubeanic acid was present. Moreover, the chlortetracycline (CTC) staining for localization of free calcium marked the wall of the idioblasts and the wall of the cells near vascular bundles. In April petiole samples, moving towards the youngest nodes, the raphydes idioblast decreased in number and in the length of the single raphydes. Besides, crystals stained with rubeanic acid appeared in the vacuoles of some cells. In June samples, numerous raphyde idioblasts oriented parallel to vascular bundles were evident. Under the electron microscope, numerous idioblasts presented not homogeneous electrondense aggregates of material, in which a few crystals (styloids) in the form of regular holes were scattered. In July samples, an increase in the number of styloid idioblasts in the youngest nodes and little masses stained with CTC near styloids were observed. Peculiar cells stained with rubeanic acid were detected and hypothesized to be involved in the formation of the idioblasts. In conclusion, in Actinidia leaves and petioles, it seems to confirm the hypothesis that the formation of styloid idioblasts can be correlated to increasing calcium levels in growing tissues.

Keywords: calcium oxalate crystals, actinidia deliciosa, light and electron microscopy, idioblasts

Procedia PDF Downloads 53
33 Organic Rankine Cycles (ORC) for Mobile Applications: Economic Feasibility in Different Transportation Sectors

Authors: Roberto Pili, Alessandro Romagnoli, Hartmut Spliethoff, Christoph Wieland

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Internal combustion engines (ICE) are today the most common energy system to drive vehicles and transportation systems. Numerous studies state that 50-60% of the fuel energy content is lost to the ambient as sensible heat. ORC offers a valuable alternative to recover such waste heat from ICE, leading to fuel energy savings and reduced emissions. In contrast, the additional weight of the ORC affects the net energy balance of the overall system and the ORC occupies additional volume that competes with vehicle transportation capacity. Consequently, a lower income from delivered freight or passenger tickets can be achieved. The economic feasibility of integrating an ORC into an ICE and the resulting economic impact of weight and volume have not been analyzed in open literature yet. This work intends to define such a benchmark for ORC applications in the transportation sector and investigates the current situation on the market. The applied methodology refers to the freight market, but it can be extended to passenger transportation as well. The economic parameter X is defined as the ratio between the variation of the freight revenues and the variation of fuel costs when an ORC is installed as a bottoming cycle for an ICE with respect to a reference case without ORC. A good economic situation is obtained when the reduction in fuel costs is higher than the reduction of revenues for the delivered freight, i.e. X<1. Through this constraint, a maximum allowable change of transport capacity for a given relative reduction in fuel consumption is determined. The specific fuel consumption is influenced by the ORC in two ways. Firstly because the transportable freight is reduced and secondly because the total weight of the vehicle is increased. Note, that the generated electricity of the ORC influences the size of the ICE and the fuel consumption as well. Taking the above dependencies into account, the limiting condition X = 1 results in a second order equation for the relative change in transported cargo. The described procedure is carried out for a typical city bus, a truck of 24-40 t of payload capacity, a middle-size freight train (1000 t), an inland water vessel (Va RoRo, 2500 t) and handysize-like vessel (25000 t). The maximum allowable mass and volume of the ORC are calculated in dependence of its efficiency in order to satisfy X < 1. Subsequently, these values are compared with weight and volume of commercial ORC products. For ships of any size, the situation appears already highly favorable. A different result is obtained for road and rail vehicles. For trains, the mass and the volume of common ORC products have to be reduced at least by 50%. For trucks and buses, the situation looks even worse. The findings of the present study show a theoretical and practical approach for the economic application of ORC in the transportation sector. In future works, the potential for volume and mass reduction of the ORC will be addressed, together with the integration of an economic assessment for the ORC.

Keywords: ORC, transportation, volume, weight

Procedia PDF Downloads 200
32 The High Potential and the Little Use of Brazilian Class Actions for Prevention and Penalization Due to Workplace Accidents in Brazil

Authors: Sandra Regina Cavalcante, Rodolfo A. G. Vilela

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Introduction: Work accidents and occupational diseases are a big problem for public health around the world and the main health problem of workers with high social and economic costs. Brazil has shown progress over the last years, with the development of the regulatory system to improve safety and quality of life in the workplace. However, the situation is far from acceptable, because the occurrences remain high and there is a great gap between legislation and reality, generated by the low level of voluntary compliance with the law. Brazilian laws provide procedural legal instruments for both, to compensate the damage caused to the worker's health and to prevent future injuries. In the Judiciary, the prevention idea is in the collective action, effected through Brazilian Class Actions. Inhibitory guardianships may impose both, improvements to the working environment, as well as determine the interruption of activity or a ban on the machine that put workers at risk. Both the Labor Prosecution and trade unions have to stand to promote this type of action, providing payment of compensation for collective moral damage. Objectives: To verify how class actions (known as ‘public civil actions’), regulated in Brazilian legal system to protect diffuse, collective and homogeneous rights, are being used to protect workers' health and safety. Methods: The author identified and evaluated decisions of Brazilian Superior Court of Labor involving collective actions and work accidents. The timeframe chosen was December 2015. The online jurisprudence database was consulted in page available for public consultation on the court website. The categorization of the data was made considering the result (court application was rejected or accepted), the request type, the amount of compensation and the author of the cause, besides knowing the reasoning used by the judges. Results: The High Court issued 21,948 decisions in December 2015, with 1448 judgments (6.6%) about work accidents and only 20 (0.09%) on collective action. After analyzing these 20 decisions, it was found that the judgments granted compensation for collective moral damage (85%) and/or obligation to make, that is, changes to improve prevention and safety (71%). The processes have been filed mainly by the Labor Prosecutor (83%), and also appeared lawsuits filed by unions (17%). The compensation for collective moral damage had average of 250,000 reais (about US$65,000), but it should be noted that there is a great range of values found, also are several situations repaired by this compensation. This is the last instance resource for this kind of lawsuit and all decisions were well founded and received partially the request made for working environment protection. Conclusions: When triggered, the labor court system provides the requested collective protection in class action. The values of convictions arbitrated in collective actions are significant and indicate that it creates social and economic repercussions, stimulating employers to improve the working environment conditions of their companies. It is necessary to intensify the use of collective actions, however, because they are more efficient for prevention than reparatory individual lawsuits, but it has been underutilized, mainly by Unions.

Keywords: Brazilian Class Action, collective action, work accident penalization, workplace accident prevention, workplace protection law

Procedia PDF Downloads 239
31 Lignin Valorization: Techno-Economic Analysis of Three Lignin Conversion Routes

Authors: Iris Vural Gursel, Andrea Ramirez

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Effective utilization of lignin is an important mean for developing economically profitable biorefineries. Current literature suggests that large amounts of lignin will become available in second generation biorefineries. New conversion technologies will, therefore, be needed to carry lignin transformation well beyond combustion to produce energy, but towards high-value products such as chemicals and transportation fuels. In recent years, significant progress on catalysis has been made to improve transformation of lignin, and new catalytic processes are emerging. In this work, a techno-economic assessment of two of these novel conversion routes and comparison with more established lignin pyrolysis route were made. The aim is to provide insights into the potential performance and potential hotspots in order to guide the experimental research and ease the commercialization by early identifying cost drivers, strengths, and challenges. The lignin conversion routes selected for detailed assessment were: (non-catalytic) lignin pyrolysis as the benchmark, direct hydrodeoxygenation (HDO) of lignin and hydrothermal lignin depolymerisation. Products generated were mixed oxygenated aromatic monomers (MOAMON), light organics, heavy organics, and char. For the technical assessment, a basis design followed by process modelling in Aspen was done using experimental yields. A design capacity of 200 kt/year lignin feed was chosen that is equivalent to a 1 Mt/y scale lignocellulosic biorefinery. The downstream equipment was modelled to achieve the separation of the product streams defined. For determining external utility requirement, heat integration was considered and when possible gasses were combusted to cover heating demand. The models made were used in generating necessary data on material and energy flows. Next, an economic assessment was carried out by estimating operating and capital costs. Return on investment (ROI) and payback period (PBP) were used as indicators. The results of the process modelling indicate that series of separation steps are required. The downstream processing was found especially demanding in the hydrothermal upgrading process due to the presence of significant amount of unconverted lignin (34%) and water. Also, external utility requirements were found to be high. Due to the complex separations, hydrothermal upgrading process showed the highest capital cost (50 M€ more than benchmark). Whereas operating costs were found the highest for the direct HDO process (20 M€/year more than benchmark) due to the use of hydrogen. Because of high yields to valuable heavy organics (32%) and MOAMON (24%), direct HDO process showed the highest ROI (12%) and the shortest PBP (5 years). This process is found feasible with a positive net present value. However, it is very sensitive to the prices used in the calculation. The assessments at this stage are associated with large uncertainties. Nevertheless, they are useful for comparing alternatives and identifying whether a certain process should be given further consideration. Among the three processes investigated here, the direct HDO process was seen to be the most promising.

Keywords: biorefinery, economic assessment, lignin conversion, process design

Procedia PDF Downloads 237
30 Peculiarities of Absorption near the Edge of the Fundamental Band of Irradiated InAs-InP Solid Solutions

Authors: Nodar Kekelidze, David Kekelidze, Elza Khutsishvili, Bela Kvirkvelia

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The semiconductor devices are irreplaceable elements for investigations in Space (artificial Earth satellite, interplanetary space craft, probes, rockets) and for investigation of elementary particles on accelerators, for atomic power stations, nuclear reactors, robots operating on heavily radiation contaminated territories (Chernobyl, Fukushima). Unfortunately, the most important parameters of semiconductors dramatically worsen under irradiation. So creation of radiation-resistant semiconductor materials for opto and microelectronic devices is actual problem, as well as investigation of complicated processes developed in irradiated solid states. Homogeneous single crystals of InP-InAs solid solutions were grown with zone melting method. There has been studied the dependence of the optical absorption coefficient vs photon energy near fundamental absorption edge. This dependence changes dramatically with irradiation. The experiments were performed on InP, InAs and InP-InAs solid solutions before and after irradiation with electrons and fast neutrons. The investigations of optical properties were carried out on infrared spectrophotometer in temperature range of 10K-300K and 1mkm-50mkm spectral area. Radiation fluencies of fast neutrons was equal to 2·1018neutron/cm2 and electrons with 3MeV, 50MeV up to fluxes of 6·1017electron/cm2. Under irradiation, there has been revealed the exponential type of the dependence of the optical absorption coefficient vs photon energy with energy deficiency. The indicated phenomenon takes place at high and low temperatures as well at impurity different concentration and practically in all cases of irradiation by various energy electrons and fast neutrons. We have developed the common mechanism of this phenomenon for unirradiated materials and implemented the quantitative calculations of distinctive parameter; this is in a satisfactory agreement with experimental data. For the irradiated crystals picture get complicated. In the work, the corresponding analysis is carried out. It has been shown, that in the case of InP, irradiated with electrons (Ф=1·1017el/cm2), the curve of optical absorption is shifted to lower energies. This is caused by appearance of the tails of density of states in forbidden band due to local fluctuations of ionized impurity (defect) concentration. Situation is more complicated in the case of InAs and for solid solutions with composition near to InAs when besides noticeable phenomenon there takes place Burstein effect caused by increase of electrons concentration as a result of irradiation. We have shown, that in certain conditions it is possible the prevalence of Burstein effect. This causes the opposite effect: the shift of the optical absorption edge to higher energies. So in given solid solutions there take place two different opposite directed processes. By selection of solid solutions composition and doping impurity we obtained such InP-InAs, solid solution in which under radiation mutual compensation of optical absorption curves displacement occurs. Obtained result let create on the base of InP-InAs, solid solution radiation-resistant optical materials. Conclusion: It was established the nature of optical absorption near fundamental edge in semiconductor materials and it was created radiation-resistant optical material.

Keywords: InAs-InP, electrons concentration, irradiation, solid solutions

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29 Finite Element Modeling of Global Ti-6Al-4V Mechanical Behavior in Relationship with Microstructural Parameters

Authors: Fatna Benmessaoud, Mohammed Cheikh, Vencent Velay, Vanessa Vedal, Farhad Rezai-Aria, Christine Boher

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The global mechanical behavior of materials is strongly linked to their microstructure, especially their crystallographic texture and their grains morphology. These material aspects determine the mechanical fields character (heterogeneous or homogeneous), thus, they give to the global behavior a degree of anisotropy according the initial microstructure. For these reasons, the prediction of global behavior of materials in relationship with the microstructure must be performed with a multi-scale approach. Therefore, multi-scale modeling in the context of crystal plasticity is widely used. In this present contribution, a phenomenological elasto-viscoplastic model developed in the crystal plasticity context and finite element method are used to investigate the effects of crystallographic texture and grains sizes on global behavior of a polycrystalline equiaxed Ti-6Al-4V alloy. The constitutive equations of this model are written on local scale for each slip system within each grain while the strain and stress mechanical fields are investigated at the global scale via finite element scale transition. The beta phase of Ti-6Al-4V alloy modeled is negligible; its percent is less than 10%. Three families of slip systems of alpha phase are considered: basal and prismatic families with a burgers vector and pyramidal family with a burgers vector. The twinning mechanism of plastic strain is not observed in Ti-6Al-4V, therefore, it is not considered in the present modeling. Nine representative elementary volumes (REV) are generated with Voronoi tessellations. For each individual equiaxed grain, the own crystallographic orientation vis-à-vis the loading is taken into account. The meshing strategy is optimized in a way to eliminate the meshing effects and at the same time to allow calculating the individual grain size. The stress and strain fields are determined in each Gauss point of the mesh element. A post-treatment is used to calculate the local behavior (in each grain) and then by appropriate homogenization, the macroscopic behavior is calculated. The developed model is validated by comparing the numerical simulation results with an experimental data reported in the literature. It is observed that the present model is able to predict the global mechanical behavior of Ti-6Al-4V alloy and investigate the microstructural parameters' effects. According to the simulations performed on the generated volumes (REV), the macroscopic mechanical behavior of Ti-6Al-4V is strongly linked to the active slip systems family (prismatic, basal or pyramidal). The crystallographic texture determines which family of slip systems can be activated; therefore it gives to the plastic strain a heterogeneous character thus an anisotropic macroscopic mechanical behavior. The average grains size influences also the Ti-6Al-4V mechanical proprieties, especially the yield stress; by decreasing of the average grains size, the yield strength increases according to Hall-Petch relationship. The grains sizes' distribution gives to the strain fields considerable heterogeneity. By increasing grain sizes, the scattering in the localization of plastic strain is observed, thus, in certain areas the stress concentrations are stronger than other regions.

Keywords: microstructural parameters, multi-scale modeling, crystal plasticity, Ti-6Al-4V alloy

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28 The Effect of Framework Structure on N2O Formation over Cu-Based Zeolites during NH3-SCR Reactions

Authors: Ghodsieh Isapour Toutizad, Aiyong Wang, Joonsoo Han, Derek Creaser, Louise Olsson, Magnus Skoglundh, Hanna HaRelind

Abstract:

Nitrous oxide (N2O), which is generally formed as a byproduct of industrial chemical processes and fossil fuel combustion, has attracted considerable attention due to its destructive role in global warming and ozone layer depletion. From various developed technologies used for lean NOx reduction, the selective catalytic reduction (SCR) of NOx with ammonia is presently the most applied method. Therefore, the development of catalysts for efficient lean NOx reduction without forming N2O in the process, or only forming it to a very small extent from the exhaust gases is of crucial significance. One type of catalysts that nowadays are used for this aim are zeolite-based catalysts. It is owing to their remarkable catalytic performance under practical reaction conditions such as high thermal stability and high N2 selectivity. Among all zeolites, copper ion-exchanged zeolites, with CHA, MFI, and BEA framework structure (like SSZ-13, ZSM-5 and Beta, respectively), represent higher hydrothermal stability, high activity and N2 selectivity. This work aims at investigating the effect of the zeolite framework structure on the formation of N2O during NH3-SCR reaction conditions over three Cu-based zeolites ranging from small-pore to large-pore framework structure. In the zeolite framework, Cu exists in two cationic forms, that can catalyze the SCR reaction by activating NO to form NO+ and/or surface nitrate species. The nitrate species can thereafter react with NH3 to form another intermediate, ammonium nitrate, which seems to be one source for N2O formation at low temperatures. The results from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) indicate that during the NO oxidation step, mainly NO+ and nitrate species are formed on the surface of the catalysts. The intensity of the absorption peak attributed to NO+ species is higher for the Cu-CHA sample compared to the other two samples, indicating a higher stability of this species in small cages. Furthermore, upon the addition of NH3, through the standard SCR reaction conditions, absorption peaks assigned to N-H stretching and bending vibrations are building up. At the same time, negative peaks are evolving in the O-H stretching region, indicating blocking/replacement of surface OH-groups by NH3 and NH4+. By removing NH3 and adding NO2 to the inlet gas composition, the peaks in the N-H stretching and bending vibration regions show a decreasing trend in intensity, with the decrease being more pronounced for increasing pore size. It can probably be owing to the higher accumulation of ammonia species in the small-pore size zeolite compared to the other two samples. Furthermore, it is worth noting that the ammonia surface species are strongly bonded to the CHA zeolite structure, which makes it more difficult to react with NO2. To conclude, the framework structure of the zeolite seems to play an important role in the formation and reactivity of surface species relevant for the SCR process. Here we intend to discuss the connection between the zeolite structure, the surface species, and the formation of N2O during ammonia-SCR.

Keywords: fast SCR, nitrous oxide, NOx, standard SCR, zeolites

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27 Improved Morphology in Sequential Deposition of the Inverted Type Planar Heterojunction Solar Cells Using Cheap Additive (DI-H₂O)

Authors: Asmat Nawaz, Ceylan Zafer, Ali K. Erdinc, Kaiying Wang, M. Nadeem Akram

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Hybrid halide Perovskites with the general formula ABX₃, where X = Cl, Br or I, are considered as an ideal candidates for the preparation of photovoltaic devices. The most commonly and successfully used hybrid halide perovskite for photovoltaic applications is CH₃NH₃PbI₃ and its analogue prepared from lead chloride, commonly symbolized as CH₃NH₃PbI₃_ₓClₓ. Some researcher groups are using lead free (Sn replaces Pb) and mixed halide perovskites for the fabrication of the devices. Both mesoporous and planar structures have been developed. By Comparing mesoporous structure in which the perovskite materials infiltrate into mesoporous metal oxide scaffold, the planar architecture is much simpler and easy for device fabrication. In a typical perovskite solar cell, a perovskite absorber layer is sandwiched between the hole and electron transport. Upon the irradiation, carriers are created in the absorber layer that can travel through hole and electron transport layers and the interface in between. We fabricated inverted planar heterojunction structure ITO/PEDOT/ Perovskite/PCBM/Al, based solar cell via two-step spin coating method. This is also called Sequential deposition method. A small amount of cheap additive H₂O was added into PbI₂/DMF to make a homogeneous solution. We prepared four different solution such as (W/O H₂O, 1% H₂O, 2% H₂O, 3% H₂O). After preparing, the whole night stirring at 60℃ is essential for the homogenous precursor solutions. We observed that the solution with 1% H₂O was much more homogenous at room temperature as compared to others. The solution with 3% H₂O was precipitated at once at room temperature. The four different films of PbI₂ were formed on PEDOT substrates by spin coating and after that immediately (before drying the PbI₂) the substrates were immersed in the methyl ammonium iodide solution (prepared in isopropanol) for the completion of the desired perovskite film. After getting desired films, rinse the substrates with isopropanol to remove the excess amount of methyl ammonium iodide and finally dried it on hot plate only for 1-2 minutes. In this study, we added H₂O in the PbI₂/DMF precursor solution. The concept of additive is widely used in the bulk- heterojunction solar cells to manipulate the surface morphology, leading to the enhancement of the photovoltaic performance. There are two most important parameters for the selection of additives. (a) Higher boiling point w.r.t host material (b) good interaction with the precursor materials. We observed that the morphology of the films was improved and we achieved a denser, uniform with less cavities and almost full surface coverage films but only using precursor solution having 1% H₂O. Therefore, we fabricated the complete perovskite solar cell by sequential deposition technique with precursor solution having 1% H₂O. We concluded that with the addition of additives in the precursor solutions one can easily be manipulate the morphology of the perovskite film. In the sequential deposition method, thickness of perovskite film is in µm and the charge diffusion length of PbI₂ is in nm. Therefore, by controlling the thickness using other deposition methods for the fabrication of solar cells, we can achieve the better efficiency.

Keywords: methylammonium lead iodide, perovskite solar cell, precursor composition, sequential deposition

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26 Chemical Synthesis and Microwave Sintering of SnO2-Based Nanoparticles for Varistor Films

Authors: Glauco M. M. M. Lustosa, João Paulo C. Costa, Leinig Antônio Perazolli, Maria Aparecida Zaghete

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SnO2 has electrical conductivity due to the excess of electrons and structural defects, being its electrical behavior highly dependent on sintering temperature and chemical composition. The addition of metals modifiers into the crystalline structure can improve and controlling the behavior of some semiconductor oxides that can therefore develop different applications such as varistors (ceramic with non-ohmic behavior between current and voltage, i.e. conductive during normal operation and resistive during overvoltage). The polymeric precursor method, based on the complexation reaction between metal ion and policarboxylic acid and then polymerized with ethylene glycol, was used to obtain nanopowders ceramic. The metal immobilization reduces its segregation during the decomposition of the polyester resulting in a crystalline oxide with high chemical homogeneity. The preparation of films from ceramics nanoparticles using electrophoretic deposition method (EPD) brings prospects for a new generation of smaller size devices with easy integration technology. EPD allows to control time and current and therefore it can have control of the thickness, surface roughness and the film density, quickly and with low production costs. The sintering process is key to control size and grain boundary density of the film. In this step, there is the diffusion of metals that promote densification and control of intrinsic defects or change these defects which will form and modify the potential barrier in the grain boundary. The use of microwave oven for sintering is an advantageous process due to the fast and homogeneous heating rate, promoting the diffusion and densification without irregular grain growth. This research was done a comparative study of sintering temperature by use of zinc as modifier agent to verify the influence on sintering step aiming to promote densification and grain growth, which influences the potential barrier formation and then changed the electrical behavior. SnO2-nanoparticles were obtained with 1 %mol of ZnO + 0.05 %mol of Nb2O5 (SZN), deposited as film through EPD (voltage 2 kV, time of 10 min) on Si/Pt substrate. Sintering was made in a microwave oven at 800, 900 and 1000 °C. For complete coverage of the substrate by nanoparticles with low surface roughness and uniform thickness was added 0.02 g of solid iodine in alcoholic suspension SnO2 to increase particle surface charge. They were also used magneto in EPD system that improved the deposition rate forming a compact film. Using a scanning electron microscope of high resolution (SEM_FEG) it was observed nanoparticles with average size between 10-20 nm, after sintering the average size was 150 to 200 nm and thickness of 5 µm. Also, it was verified that the temperature at 1000 °C was the most efficient in sintering. The best sintering time was also recorded and determined as 40 minutes. After sintering, the films were recovered with Cr3+ ions layer by EPD, then the films were again thermally treated. The electrical characterizations (nonlinear coefficient of 11.4, voltage rupture of ~60 V and leakage current = 4.8x10−6 A), allow considering the new methodology suitable for prepare SnO2-based varistor applied for development of electrical protection devices for low voltage.

Keywords: chemical synthesis, electrophoretic deposition, microwave sintering, tin dioxide

Procedia PDF Downloads 238
25 Smart and Active Package Integrating Printed Electronics

Authors: Joana Pimenta, Lorena Coelho, José Silva, Vanessa Miranda, Jorge Laranjeira, Rui Soares

Abstract:

In this paper, the results of R&D on an innovative food package for increased shelf-life are presented. SAP4MA aims at the development of a printed active device that enables smart packaging solutions for food preservation, targeting the extension of the shelf-life of the packed food through the controlled release of active natural antioxidant agents at the onset of the food degradation process. To do so, SAP4MA focuses on the development of active devices such as printed heaters and batteries/supercapacitors in a label format to be integrated on packaging lids during its injection molding process, promoting the passive release of natural antioxidants after the product is packed, during transportation and in the shelves, and actively when the end-user activates the package, just prior to consuming the product at home. When the active device present on the lid is activated, the release of the natural antioxidants embedded in the inner layer of the packaging lid in direct contact with the headspace atmosphere of the food package starts. This approach is based on the use of active functional coatings composed of nano encapsulated active agents (natural antioxidants species) in the prevention of the oxidation of lipid compounds in food by agents such as oxygen. Thus keeping the product quality during the shelf-life, not only when the user opens the packaging, but also during the period from food packaging up until the purchase by the consumer. The active systems that make up the printed smart label, heating circuit, and battery were developed using screen-printing technology. These systems must operate under the working conditions associated with this application. The printed heating circuit was studied using three different substrates and two different conductive inks. Inks were selected, taking into consideration that the printed circuits will be subjected to high pressures and temperatures during the injection molding process. The circuit must reach a homogeneous temperature of 40ºC in the entire area of the lid of the food tub, promoting a gradual and controlled release of the antioxidant agents. In addition, the circuit design involves a high level of study in order to guarantee maximum performance after the injection process and meet the specifications required by the control electronics component. Furthermore, to characterize the different heating circuits, the electrical resistance promoted by the conductive ink and the circuit design, as well as the thermal behavior of printed circuits on different substrates, were evaluated. In the injection molding process, the serpentine-shaped design developed for the heating circuit was able to resolve the issues connected to the injection point; in addition, the materials used in the support and printing had high mechanical resistance against the pressure and temperature inherent to the injection process. Acknowledgment: This research has been carried out within the Project “Smart and Active Packing for Margarine Product” (SAP4MA) running under the EURIPIDES Program being co-financed by COMPETE 2020 – the Operational Programme for Competitiveness and Internationalization and under Portugal 2020 through the European Regional Development Fund (ERDF).

Keywords: smart package, printed heat circuits, printed batteries, flexible and printed electronic

Procedia PDF Downloads 79
24 Safety Considerations of Furanics for Sustainable Applications in Advanced Biorefineries

Authors: Anitha Muralidhara, Victor Engelen, Christophe Len, Pascal Pandard, Guy Marlair

Abstract:

Production of bio-based chemicals and materials from lignocellulosic biomass is gaining tremendous importance in advanced bio-refineries while aiming towards progressive replacement of petroleum based chemicals in transportation fuels and commodity polymers. One such attempt has resulted in the production of key furan derivatives (FD) such as furfural, HMF, MMF etc., via acid catalyzed dehydration (ACD) of C6 and C5 sugars, which are further converted into key chemicals or intermediates (such as Furandicarboxylic acid, Furfuryl alcohol etc.,). In subsequent processes, many high potential FD are produced, that can be converted into high added value polymers or high energy density biofuels. During ACD, an unavoidable polyfuranic byproduct is generated which is called humins. The family of FD is very large with varying chemical structures and diverse physicochemical properties. Accordingly, the associated risk profiles may largely vary. Hazardous Material (Haz-mat) classification systems such as GHS (CLP in the EU) and the UN TDG Model Regulations for transport of dangerous goods are one of the preliminary requirements for all chemicals for their appropriate classification, labelling, packaging, safe storage, and transportation. Considering the growing application routes of FD, it becomes important to notice the limited access to safety related information (safety data sheets available only for famous compounds such as HMF, furfural etc.,) in these internationally recognized haz-mat classification systems. However, these classifications do not necessarily provide information about the extent of risk involved when the chemical is used in any specific application. Factors such as thermal stability, speed of combustion, chemical incompatibilities, etc., can equally influence the safety profile of a compound, that are clearly out of the scope of any haz-mat classification system. Irrespective of the bio-based origin, FD has so far received inconsistent remarks concerning their toxicity profiles. With such inconsistencies, there is a fear that, a large family of FD may also follow extreme judgmental scenarios like ionic liquids, by ranking some compounds as extremely thermally stable, non-flammable, etc., Unless clarified, these messages could lead to misleading judgements while ranking the chemical based on its hazard rating. Safety is a key aspect in any sustainable biorefinery operation/facility, which is often underscored or neglected. To fill up these existing data gaps and to address ambiguities and discrepancies, the current study focuses on giving preliminary insights on safety assessment of FD and their potential targeted by-products. With the available information in the literature and obtained experimental results, physicochemical safety, environmental safety as well as (a scenario based) fire safety profiles of key FD, as well as side streams such as humins and levulinic acid, will be considered. With this, the study focuses on defining patterns and trends that gives coherent safety related information for existing and newly synthesized FD in the market for better functionality and sustainable applications.

Keywords: furanics, humins, safety, thermal and fire hazard, toxicity

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23 Digital Holographic Interferometric Microscopy for the Testing of Micro-Optics

Authors: Varun Kumar, Chandra Shakher

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Micro-optical components such as microlenses and microlens array have numerous engineering and industrial applications for collimation of laser diodes, imaging devices for sensor system (CCD/CMOS, document copier machines etc.), for making beam homogeneous for high power lasers, a critical component in Shack-Hartmann sensor, fiber optic coupling and optical switching in communication technology. Also micro-optical components have become an alternative for applications where miniaturization, reduction of alignment and packaging cost are necessary. The compliance with high-quality standards in the manufacturing of micro-optical components is a precondition to be compatible on worldwide markets. Therefore, high demands are put on quality assurance. For quality assurance of these lenses, an economical measurement technique is needed. For cost and time reason, technique should be fast, simple (for production reason), and robust with high resolution. The technique should provide non contact, non-invasive and full field information about the shape of micro- optical component under test. The interferometric techniques are noncontact type and non invasive and provide full field information about the shape of the optical components. The conventional interferometric technique such as holographic interferometry or Mach-Zehnder interferometry is available for characterization of micro-lenses. However, these techniques need more experimental efforts and are also time consuming. Digital holography (DH) overcomes the above described problems. Digital holographic microscopy (DHM) allows one to extract both the amplitude and phase information of a wavefront transmitted through the transparent object (microlens or microlens array) from a single recorded digital hologram by using numerical methods. Also one can reconstruct the complex object wavefront at different depths due to numerical reconstruction. Digital holography provides axial resolution in nanometer range while lateral resolution is limited by diffraction and the size of the sensor. In this paper, Mach-Zehnder based digital holographic interferometric microscope (DHIM) system is used for the testing of transparent microlenses. The advantage of using the DHIM is that the distortions due to aberrations in the optical system are avoided by the interferometric comparison of reconstructed phase with and without the object (microlens array). In the experiment, first a digital hologram is recorded in the absence of sample (microlens array) as a reference hologram. Second hologram is recorded in the presence of microlens array. The presence of transparent microlens array will induce a phase change in the transmitted laser light. Complex amplitude of object wavefront in presence and absence of microlens array is reconstructed by using Fresnel reconstruction method. From the reconstructed complex amplitude, one can evaluate the phase of object wave in presence and absence of microlens array. Phase difference between the two states of object wave will provide the information about the optical path length change due to the shape of the microlens. By the knowledge of the value of the refractive index of microlens array material and air, the surface profile of microlens array is evaluated. The Sag of microlens and radius of curvature of microlens are evaluated and reported. The sag of microlens agrees well within the experimental limit as provided in the specification by the manufacturer.

Keywords: micro-optics, microlens array, phase map, digital holographic interferometric microscopy

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22 Biomass Waste-To-Energy Technical Feasibility Analysis: A Case Study for Processing of Wood Waste in Malta

Authors: G. A. Asciak, C. Camilleri, A. Rizzo

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The waste management in Malta is a national challenge. Coupled with Malta’s recent economic boom, which has seen massive growth in several sectors, especially the construction industry, drastic actions need to be taken. Wood waste, currently being dumped in landfills, is one type of waste which has increased astronomically. This research study aims to carry out a thorough examination on the possibility of using this waste as a biomass resource and adopting a waste-to-energy technology in order to generate electrical energy. This study is composed of three distinct yet interdependent phases, namely, data collection from the local SMEs, thermal analysis using the bomb calorimeter, and generation of energy from wood waste using a micro biomass plant. Data collection from SMEs specializing in wood works was carried out to obtain information regarding the available types of wood waste, the annual weight of imported wood, and to analyse the manner in which wood shavings are used after wood is manufactured. From this analysis, it resulted that five most common types of wood available in Malta which would suitable for generating energy are Oak (hardwood), Beech (hardwood), Red Beech (softwood), African Walnut (softwood) and Iroko (hardwood). Subsequently, based on the information collected, a thermal analysis using a 6200 Isoperibol calorimeter on the five most common types of wood was performed. This analysis was done so as to give a clear indication with regards to the burning potential, which will be valuable when testing the wood in the biomass plant. The experiments carried out in this phase provided a clear indication that the African Walnut generated the highest gross calorific value. This means that this type of wood released the highest amount of heat during the combustion in the calorimeter. This is due to the high presence of extractives and lignin, which accounts for a slightly higher gross calorific value. This is followed by Red Beech and Oak. Moreover, based on the findings of the first phase, both the African Walnut and Red Beech are highly imported in the Maltese Islands for use in various purposes. Oak, which has the third highest gross calorific value is the most imported and common wood used. From the five types of wood, three were chosen for use in the power plant on the basis of their popularity and their heating values. The PP20 biomass plant was used to burn the three types of shavings in order to compare results related to the estimated feedstock consumed by the plant, the high temperatures generated, the time taken by the plant to produce gasification temperatures, and the projected electrical power attributed to each wood type. From the experiments, it emerged that whilst all three types reached the required gasification temperature and thus, are feasible for electrical energy generation. African Walnut was deemed to be the most suitable fast-burning fuel. This is followed by Red-beech and Oak, which required a longer period of time to reach the required gasification temperatures. The results obtained provide a clear indication that wood waste can not only be treated instead of being dumped in dumped in landfill but coupled.

Keywords: biomass, isoperibol calorimeter, waste-to-energy technology, wood

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21 Rheological and Microstructural Characterization of Concentrated Emulsions Prepared by Fish Gelatin

Authors: Helen S. Joyner (Melito), Mohammad Anvari

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Concentrated emulsions stabilized by proteins are systems of great importance in food, pharmaceutical and cosmetic products. Controlling emulsion rheology is critical for ensuring desired properties during formation, storage, and consumption of emulsion-based products. Studies on concentrated emulsions have focused on rheology of monodispersed systems. However, emulsions used for industrial applications are polydispersed in nature, and this polydispersity is regarded as an important parameter that also governs the rheology of the concentrated emulsions. Therefore, the objective of this study was to characterize rheological (small and large deformation behaviors) and microstructural properties of concentrated emulsions which were not truly monodispersed as usually encountered in food products such as margarines, mayonnaise, creams, spreads, and etc. The concentrated emulsions were prepared at different concentrations of fish gelatin (0.2, 0.4, 0.8% w/v in the whole emulsion system), oil-water ratio 80-20 (w/w), homogenization speed 10000 rpm, and 25oC. Confocal laser scanning microscopy (CLSM) was used to determine the microstructure of the emulsions. To prepare samples for CLSM analysis, FG solutions were stained by Fluorescein isothiocyanate dye. Emulsion viscosity profiles were determined using shear rate sweeps (0.01 to 100 1/s). The linear viscoelastic regions (LVRs) of the emulsions were determined using strain sweeps (0.01 to 100% strain) for each sample. Frequency sweeps were performed in the LVR (0.1% strain) from 0.6 to 100 rad/s. Large amplitude oscillatory shear (LAOS) testing was conducted by collecting raw waveform data at 0.05, 1, 10, and 100% strain at 4 different frequencies (0.5, 1, 10, and 100 rad/s). All measurements were performed in triplicate at 25oC. The CLSM results revealed that increased fish gelatin concentration resulted in more stable oil-in-water emulsions with homogeneous, finely dispersed oil droplets. Furthermore, the protein concentration had a significant effect on emulsion rheological properties. Apparent viscosity and dynamic moduli at small deformations increased with increasing fish gelatin concentration. These results were related to increased inter-droplet network connections caused by increased fish gelatin adsorption at the surface of oil droplets. Nevertheless, all samples showed shear-thinning and weak gel behaviors over shear rate and frequency sweeps, respectively. Lissajous plots, or plots of stress versus strain, and phase lag values were used to determine nonlinear behavior of the emulsions in LAOS testing. Greater distortion in the elliptical shape of the plots followed by higher phase lag values was observed at large strains and frequencies in all samples, indicating increased nonlinear behavior. Shifts from elastic-dominated to viscous dominated behavior were also observed. These shifts were attributed to damage to the sample microstructure (e.g. gel network disruption), which would lead to viscous-type behaviors such as permanent deformation and flow. Unlike the small deformation results, the LAOS behavior of the concentrated emulsions was not dependent on fish gelatin concentration. Systems with different microstructures showed similar nonlinear viscoelastic behaviors. The results of this study provided valuable information that can be used to incorporate concentrated emulsions in emulsion-based food formulations.

Keywords: concentrated emulsion, fish gelatin, microstructure, rheology

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20 Analysis of Flow Dynamics of Heated and Cooled Pylon Upstream to the Cavity past Supersonic Flow with Wall Heating and Cooling

Authors: Vishnu Asokan, Zaid M. Paloba

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Flow over cavities is an important area of research due to the significant change in flow physics caused by cavity aspect ratio, free stream Mach number and the nature of upstream boundary layer approaching the cavity leading edge. Cavity flow finds application in aircraft wheel well, weapons bay, combustion chamber of scramjet engines, etc. These flows are highly unsteady, compressible and turbulent and it involves mass entrainment coupled with acoustics phenomenon. Variation of flow dynamics in an angled cavity with a heated and cooled pylon upstream to the cavity with spatial combinations of heat flux addition and removal to the wall studied numerically. The goal of study is to investigate the effect of energy addition, removal to the cavity walls and pylon cavity flow dynamics. Preliminary steady state numerical simulations on inclined cavities with heat addition have shown that wall pressure profiles, as well as the recirculation, are influenced by heat transfer to the compressible fluid medium. Such a hybrid control of cavity flow dynamics in the form of heat transfer and pylon geometry can open out greater opportunities in enhancement of mixing and flame holding requirements of supersonic combustors. Addition of pylon upstream to the cavity reduces the acoustic oscillations emanating from the geometry. A numerical unsteady analysis of supersonic flow past cavities exposed to cavity wall heating and cooling with heated and cooled pylon helps to get a clear idea about the oscillation suppression in the cavity. A Cavity of L/D 4 and aft wall angle 22 degree with an upstream pylon of h/D=1.5 mm with a wall angle 29 degree exposed to supersonic flow of Mach number 2 and heat flux of 40 W/cm² and -40 W/cm² modeled for the above study. In the preliminary study, the domain is modeled and validated numerically with a turbulence model of SST k-ω using an HLLC implicit scheme. Both qualitative and quantitative flow data extracted and analyzed using advanced CFD tools. Flow visualization is done using numerical Schlieren method as the fluid medium gives the density variation. The heat flux addition to the wall increases the secondary vortex size of the cavity and removal of energy leads to the reduction in vortex size. The flow field turbulence seems to be increasing at higher heat flux. The shear layer thickness increases as heat flux increases. The steady state analysis of wall pressure shows that there is variation on wall pressure as heat flux increases. Shift in frequency of unsteady wall pressure analysis is an interesting observation for the above study. The time averaged skin friction seems to be reducing at higher heat flux due to the variation in viscosity of fluid inside the cavity.

Keywords: energy addition, frequency shift, Numerical Schlieren, shear layer, vortex evolution

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19 Rapid Atmospheric Pressure Photoionization-Mass Spectrometry (APPI-MS) Method for the Detection of Polychlorinated Dibenzo-P-Dioxins and Dibenzofurans in Real Environmental Samples Collected within the Vicinity of Industrial Incinerators

Authors: M. Amo, A. Alvaro, A. Astudillo, R. Mc Culloch, J. C. del Castillo, M. Gómez, J. M. Martín

Abstract:

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of course comprise a range of highly toxic compounds that may exist as particulates within the air or accumulate within water supplies, soil, or vegetation. They may be created either ubiquitously or naturally within the environment as a product of forest fires or volcanic eruptions. It is only since the industrial revolution, however, that it has become necessary to closely monitor their generation as a byproduct of manufacturing/combustion processes, in an effort to mitigate widespread contamination events. Of course, the environmental concentrations of these toxins are expected to be extremely low, therefore highly sensitive and accurate methods are required for their determination. Since ionization of non-polar compounds through electrospray and APCI is difficult and inefficient, we evaluate the performance of a novel low-flow Atmospheric Pressure Photoionization (APPI) source for the trace detection of various dioxins and furans using rapid Mass Spectrometry workflows. Air, soil and biota (vegetable matter) samples were collected monthly during one year from various locations within the vicinity of an industrial incinerator in Spain. Analytes were extracted and concentrated using soxhlet extraction in toluene and concentrated by rotavapor and nitrogen flow. Various ionization methods as electrospray (ES) and atmospheric pressure chemical ionization (APCI) were evaluated, however, only the low-flow APPI source was capable of providing the necessary performance, in terms of sensitivity, required for detecting all targeted analytes. In total, 10 analytes including 2,3,7,8-tetrachlorodibenzodioxin (TCDD) were detected and characterized using the APPI-MS method. Both PCDDs and PCFDs were detected most efficiently in negative ionization mode. The most abundant ion always corresponded to the loss of a chlorine and addition of an oxygen, yielding [M-Cl+O]- ions. MRM methods were created in order to provide selectivity for each analyte. No chromatographic separation was employed; however, matrix effects were determined to have a negligible impact on analyte signals. Triple Quadrupole Mass Spectrometry was chosen because of its unique potential for high sensitivity and selectivity. The mass spectrometer used was a Sciex´s Qtrap3200 working in negative Multi Reacting Monitoring Mode (MRM). Typically mass detection limits were determined to be near the 1-pg level. The APPI-MS2 technology applied to the detection of PCDD/Fs allows fast and reliable atmospheric analysis, minimizing considerably operational times and costs, with respect other technologies available. In addition, the limit of detection can be easily improved using a more sensitive mass spectrometer since the background in the analysis channel is very low. The APPI developed by SEADM allows polar and non-polar compounds ionization with high efficiency and repeatability.

Keywords: atmospheric pressure photoionization-mass spectrometry (APPI-MS), dioxin, furan, incinerator

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18 Case Study on Innovative Aquatic-Based Bioeconomy for Chlorella sorokiniana

Authors: Iryna Atamaniuk, Hannah Boysen, Nils Wieczorek, Natalia Politaeva, Iuliia Bazarnova, Kerstin Kuchta

Abstract:

Over the last decade due to climate change and a strategy of natural resources preservation, the interest for the aquatic biomass has dramatically increased. Along with mitigation of the environmental pressure and connection of waste streams (including CO2 and heat emissions), microalgae bioeconomy can supply food, feed, as well as the pharmaceutical and power industry with number of value-added products. Furthermore, in comparison to conventional biomass, microalgae can be cultivated in wide range of conditions without compromising food and feed production, thus addressing issues associated with negative social and the environmental impacts. This paper presents the state-of-the art technology for microalgae bioeconomy from cultivation process to production of valuable components and by-streams. Microalgae Chlorella sorokiniana were cultivated in the pilot-scale innovation concept in Hamburg (Germany) using different systems such as race way pond (5000 L) and flat panel reactors (8 x 180 L). In order to achieve the optimum growth conditions along with suitable cellular composition for the further extraction of the value-added components, process parameters such as light intensity, temperature and pH are continuously being monitored. On the other hand, metabolic needs in nutrients were provided by addition of micro- and macro-nutrients into a medium to ensure autotrophic growth conditions of microalgae. The cultivation was further followed by downstream process and extraction of lipids, proteins and saccharides. Lipids extraction is conducted in repeated-batch semi-automatic mode using hot extraction method according to Randall. As solvents hexane and ethanol are used at different ratio of 9:1 and 1:9, respectively. Depending on cell disruption method along with solvents ratio, the total lipids content showed significant variations between 8.1% and 13.9 %. The highest percentage of extracted biomass was reached with a sample pretreated with microwave digestion using 90% of hexane and 10% of ethanol as solvents. Proteins content in microalgae was determined by two different methods, namely: Total Kejadahl Nitrogen (TKN), which further was converted to protein content, as well as Bradford method using Brilliant Blue G-250 dye. Obtained results, showed a good correlation between both methods with protein content being in the range of 39.8–47.1%. Characterization of neutral and acid saccharides from microalgae was conducted by phenol-sulfuric acid method at two wavelengths of 480 nm and 490 nm. The average concentration of neutral and acid saccharides under the optimal cultivation conditions was 19.5% and 26.1%, respectively. Subsequently, biomass residues are used as substrate for anaerobic digestion on the laboratory-scale. The methane concentration, which was measured on the daily bases, showed some variations for different samples after extraction steps but was in the range between 48% and 55%. CO2 which is formed during the fermentation process and after the combustion in the Combined Heat and Power unit can potentially be used within the cultivation process as a carbon source for the photoautotrophic synthesis of biomass.

Keywords: bioeconomy, lipids, microalgae, proteins, saccharides

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17 Use of Sewage Sludge Ash as Partial Cement Replacement in the Production of Mortars

Authors: Domagoj Nakic, Drazen Vouk, Nina Stirmer, Mario Siljeg, Ana Baricevic

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Wastewater treatment processes generate significant quantities of sewage sludge that need to be adequately treated and disposed. In many EU countries, the problem of adequate disposal of sewage sludge has not been solved, nor is determined by the unique rules, instructions or guidelines. Disposal of sewage sludge is important not only in terms of satisfying the regulations, but the aspect of choosing the optimal wastewater and sludge treatment technology. Among the solutions that seem reasonable, recycling of sewage sludge and its byproducts reaches the top recommendation. Within the framework of sustainable development, recycling of sludge almost completely closes the cycle of wastewater treatment in which only negligible amounts of waste that requires landfilling are being generated. In many EU countries, significant amounts of sewage sludge are incinerated, resulting in a new byproduct in the form of ash. Sewage sludge ash is three to five times less in volume compared to stabilized and dehydrated sludge, but it also requires further management. The combustion process also destroys hazardous organic components in the sludge and minimizes unpleasant odors. The basic objective of the presented research is to explore the possibilities of recycling of the sewage sludge ash as a supplementary cementitious material. This is because of the main oxides present in the sewage sludge ash (SiO2, Al2O3 and Cao, which is similar to cement), so it can be considered as latent hydraulic and pozzolanic material. Physical and chemical characteristics of ashes, generated by sludge collected from different wastewater treatment plants, and incinerated in laboratory conditions at different temperatures, are investigated since it is a prerequisite of its subsequent recycling and the eventual use in other industries. Research was carried out by replacing up to 20% of cement by mass in cement mortar mixes with different obtained ashes and examining characteristics of created mixes in fresh and hardened condition. The mixtures with the highest ash content (20%) showed an average drop in workability of about 15% which is attributed to the increased water requirements when ash was used. Although some mixes containing added ash showed compressive and flexural strengths equivalent to those of reference mixes, generally slight decrease in strength was observed. However, it is important to point out that the compressive strengths always remained above 85% compared to the reference mix, while flexural strengths remained above 75%. Ecological impact of innovative construction products containing sewage sludge ash was determined by analyzing leaching concentrations of heavy metals. Results demonstrate that sewage sludge ash can satisfy technical and environmental criteria for use in cementitious materials which represents a new recycling application for an increasingly important waste material that is normally landfilled. Particular emphasis is placed on linking the composition of generated ashes depending on its origin and applied treatment processes (stage of wastewater treatment, sludge treatment technology, incineration temperature) with the characteristics of the final products. Acknowledgement: This work has been fully supported by Croatian Science Foundation under the project '7927 - Reuse of sewage sludge in concrete industry – from infrastructure to innovative construction products'.

Keywords: cement mortar, recycling, sewage sludge ash, sludge disposal

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