Search results for: net-zero emission transition
Commenced in January 2007
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Edition: International
Paper Count: 3072

Search results for: net-zero emission transition

252 Thermoplastic-Intensive Battery Trays for Optimum Electric Vehicle Battery Pack Performance

Authors: Dinesh Munjurulimana, Anil Tiwari, Tingwen Li, Carlos Pereira, Sreekanth Pannala, John Waters

Abstract:

With the rapid transition to electric vehicles (EVs) across the globe, car manufacturers are in need of integrated and lightweight solutions for the battery packs of these vehicles. An integral part of a battery pack is the battery tray, which constitutes a significant portion of the pack’s overall weight. Based on the functional requirements, cost targets, and packaging space available, a range of materials –from metals, composites, and plastics– are often used to develop these battery trays. This paper considers the design and development of integrated thermoplastic-intensive battery trays, using the available packaging space from a representative EV battery pack. Presented as a proposed alternative are multiple concepts to integrate several connected systems such as cooling plates and underbody impact protection parts of a multi-piece incumbent battery pack. The resulting digital prototype was evaluated for several mechanical performance measures such as mechanical shock, drop, crush resistance, modal analysis, and torsional stiffness. The performance of this alternative design is then compared with the incumbent solution. In addition, insights are gleaned into how these novel approaches can be optimized to meet or exceed the performance of incumbent designs. Preliminary manufacturing feasibility of the optimal solution using injection molding and other commonly used manufacturing methods for thermoplastics is briefly explained. Then numerical and analytical evaluations are performed to show a representative Pareto front of cost vs. volume of the production parts. The proposed solution is observed to offer weight savings of up to 40% on a component level and part elimination of up to two systems in the battery pack of a typical battery EV while offering the potential to meet the required performance measures highlighted above. These conceptual solutions are also observed to potentially offer secondary benefits such as improved thermal and electrical isolations and be able to achieve complex geometrical features, thus demonstrating the ability to use the complete packaging space available in the vehicle platform considered. The detailed study presented in this paper serves as a valuable reference for researches across the globe working on the development of EV battery packs – especially those with an interest in the potential of employing alternate solutions as part of a mixed-material system to help capture untapped opportunities to optimize performance and meet critical application requirements.

Keywords: thermoplastics, lightweighting, part integration, electric vehicle battery packs

Procedia PDF Downloads 193
251 Damage Tolerance of Composites Containing Hybrid, Carbon-Innegra, Fibre Reinforcements

Authors: Armin Solemanifar, Arthur Wilkinson, Kinjalkumar Patel

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Carbon fibre (CF) - polymer laminate composites have very low densities (approximately 40% lower than aluminium), high strength and high stiffness but in terms of toughness properties they often require modifications. For example, adding rubbers or thermoplastics toughening agents are common ways of improving the interlaminar fracture toughness of initially brittle thermoset composite matrices. The main aim of this project was to toughen CF-epoxy resin laminate composites using hybrid CF-fabrics incorporating Innegra™ a commercial highly-oriented polypropylene (PP) fibre, in which more than 90% of its crystal orientation is parallel to the fibre axis. In this study, the damage tolerance of hybrid (carbon-Innegra, CI) composites was investigated. Laminate composites were produced by resin-infusion using: pure CF fabric; fabrics with different ratios of commingled CI, and two different types of pure Innegra fabrics (Innegra 1 and Innegra 2). Dynamic mechanical thermal analysis (DMTA) was used to measure the glass transition temperature (Tg) of the composite matrix and values of flexural storage modulus versus temperature. Mechanical testing included drop-weight impact, compression-after-impact (CAI), and interlaminar (short-beam) shear strength (ILSS). Ultrasonic C-Scan imaging was used to determine the impact damage area and scanning electron microscopy (SEM) to observe the fracture mechanisms that occur during failure of the composites. For all composites, 8 layers of fabrics were used with a quasi-isotropic sequence of [-45°, 0°, +45°, 90°]s. DMTA showed the Tg of all composites to be approximately same (123 ±3°C) and that flexural storage modulus (before the onset of Tg) was the highest for the pure CF composite while the lowest were for the Innegra 1 and 2 composites. Short-beam shear strength of the commingled composites was higher than other composites, while for Innegra 1 and 2 composites only inelastic deformation failure was observed during the short-beam test. During impact, the Innegra 1 composite withstood up to 40 J without any perforation while for the CF perforation occurred at 10 J. The rate of reduction in compression strength upon increasing the impact energy was lowest for the Innegra 1 and 2 composites, while CF showed the highest rate. On the other hand, the compressive strength of the CF composite was highest of all the composites at all impacted energy levels. The predominant failure modes for Innegra composites observed in cross-sections of fractured specimens were fibre pull-out, micro-buckling, and fibre plastic deformation; while fibre breakage and matrix delamination were a major failure observed in the commingled composites due to the more brittle behaviour of CF. Thus, Innegra fibres toughened the CF composites but only at the expense of reducing compressive strength.

Keywords: hybrid composite, thermoplastic fibre, compression strength, damage tolerance

Procedia PDF Downloads 277
250 Development of High-Efficiency Down-Conversion Fluoride Phosphors to Increase the Efficiency of Solar Panels

Authors: S. V. Kuznetsov, M. N. Mayakova, V. Yu. Proydakova, V. V. Pavlov, A. S. Nizamutdinov, O. A. Morozov, V. V. Voronov, P. P. Fedorov

Abstract:

Increase in the share of electricity received by conversion of solar energy results in the reduction of the industrial impact on the environment from the use of the hydrocarbon energy sources. One way to increase said share is to improve the efficiency of solar energy conversion in silicon-based solar panels. Such efficiency increase can be achieved by transferring energy from sunlight-insensitive areas of work of silicon solar panels to the area of their photoresistivity. To achieve this goal, a transition to new luminescent materials with the high quantum yield of luminescence is necessary. Improvement in the quantum yield can be achieved by quantum cutting, which allows obtaining a quantum yield of down conversion of more than 150% due to the splitting of high-energy photons of the UV spectral range into lower-energy photons of the visible and near infrared spectral ranges. The goal of present work is to test approach of excitation through sensibilization of 4f-4f fluorescence of Yb3+ by various RE ions absorbing in UV and Vis spectral ranges. One of promising materials for quantum cutting luminophores are fluorides. In our investigation we have developed synthesis of nano- and submicron powders of calcium fluoride and strontium doped with rare-earth elements (Yb: Ce, Yb: Pr, Yb: Eu) of controlled dimensions and shape by co-precipitation from water solution technique. We have used Ca(NO3)2*4H2O, Sr(NO3)2, HF, NH4F as precursors. After initial solutions of nitrates were prepared they have been mixed with fluorine containing solution by dropwise manner. According to XRD data, the synthesis resulted in single phase samples with fluorite structure. By means of SEM measurements, we have confirmed spherical morphology and have determined sizes of particles (50-100 nm after synthesis and 150-300 nm after calcination). Temperature of calcination appeared to be 600°C. We have investigated the spectral-kinetic characteristics of above mentioned compounds. Here the diffuse reflection and laser induced fluorescence spectra of Yb3+ ions excited at around 4f-4f and 4f-5d transitions of Pr3+, Eu3+ and Ce3+ ions in the synthesized powders are reported. The investigation of down conversion luminescence capability of synthesized compounds included measurements of fluorescence decays and quantum yield of 2F5/2-2F7/2 fluorescence of Yb3+ ions as function of Yb3+ and sensitizer contents. An optimal chemical composition of CaF2-YbF3- LnF3 (Ln=Ce, Eu, Pr), SrF2-YbF3-LnF3 (Ln=Ce, Eu, Pr) micro- and nano- powders according to criteria of maximal IR fluorescence yield is proposed. We suppose that investigated materials are prospective in solar panels improvement applications. Work was supported by Russian Science Foundation grant #17-73- 20352.

Keywords: solar cell, fluorides, down-conversion luminescence, maximum quantum yield

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249 Estimating Industrial Pollution Load in Phnom Penh by Industrial Pollution Projection System

Authors: Vibol San, Vin Spoann

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Manufacturing plays an important role in job creation around the world. In 2013, it is estimated that there were more than half a billion jobs in manufacturing. In Cambodia in 2015, the primary industry occupies 26.18% of the total economy, while agriculture is contributing 29% and the service sector 39.43%. The number of industrial factories, which are dominated by garment and textiles, has increased since 1994, mainly in Phnom Penh city. Approximately 56% out of total 1302 firms are operated in the Capital city in Cambodia. Industrialization to achieve the economic growth and social development is directly responsible for environmental degradation, threatening the ecosystem and human health issues. About 96% of total firms in Phnom Penh city are the most and moderately polluting firms, which have contributed to environmental concerns. Despite an increasing array of laws, strategies and action plans in Cambodia, the Ministry of Environment has encountered some constraints in conducting the monitoring work, including lack of human and financial resources, lack of research documents, the limited analytical knowledge, and lack of technical references. Therefore, the necessary information on industrial pollution to set strategies, priorities and action plans on environmental protection issues is absent in Cambodia. In the absence of this data, effective environmental protection cannot be implemented. The objective of this study is to estimate industrial pollution load by employing the Industrial Pollution Projection System (IPPS), a rapid environmental management tool for assessment of pollution load, to produce a scientific rational basis for preparing future policy direction to reduce industrial pollution in Phnom Penh city. Due to lack of industrial pollution data in Phnom Penh, industrial emissions to the air, water and land as well as the sum of emissions to all mediums (air, water, land) are estimated using employment economic variable in IPPS. Due to the high number of employees, the total environmental load generated in Phnom Penh city is estimated to be 476.980.93 tons in 2014, which is the highest industrial pollution compared to other locations in Cambodia. The result clearly indicates that Phnom Penh city is the highest emitter of all pollutants in comparison with environmental pollutants released by other provinces. The total emission of industrial pollutants in Phnom Penh shares 55.79% of total industrial pollution load in Cambodia. Phnom Penh city generates 189,121.68 ton of VOC, 165,410.58 ton of toxic chemicals to air, 38,523.33 ton of toxic chemicals to land and 28,967.86 ton of SO2 in 2014. The results of the estimation show that Textile and Apparel sector is the highest generators of toxic chemicals into land and air, and toxic metals into land, air and water, while Basic Metal sector is the highest contributor of toxic chemicals to water. Textile and Apparel sector alone emits 436,015.84 ton of total industrial pollution loads. The results suggest that reduction in industrial pollution could be achieved by focusing on the most polluting sectors.

Keywords: most polluting area, polluting industry, pollution load, pollution intensity

Procedia PDF Downloads 242
248 Sustaining Efficiency in Electricity Distribution to Enhance Effective Human Security for the Vulnerable People in Ghana

Authors: Anthony Nyamekeh-Armah Adjei, Toshiaki Aoki

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The unreliable and poor efficiency of electricity distribution leading to frequent power outages and high losses are the major challenge facing the power distribution sector in Ghana. Distribution system routes electricity from the power generating station at a higher voltage through the transmission grid and steps it down through the low voltage lines to end users. Approximately all electricity problems and disturbances that have increased the call for renewable and sustainable energy in recent years have their roots in the distribution system. Therefore, sustaining electricity distribution efficiency can potentially contribute to the reserve of natural energy resources use in power generation, reducing greenhouse gas emission (GHG), decreasing tariffs for consumers and effective human security. Human Security is a people-centered approach where individual human being is the principal object of concern, focuses on protecting the vital core of all human lives in ways for meeting basic needs that enhance the safety and protection of individuals and communities. The vulnerability is the diminished capacity of an individual or group to anticipate, resist and recover from the effect of natural, human-induced disaster. The research objectives are to explore the causes of frequent power outages to consumers, high losses in the distribution network and the effect of poor electricity distribution efficiency on the vulnerable (poor and ordinary) people that mostly depend on electricity for their daily activities or life to survive. The importance of the study is that in a developing country like Ghana where raising a capital for new infrastructure project is difficult, it would be beneficial to enhance the efficiency that will significantly minimize the high energy losses, reduce power outage, to ensure safe and reliable delivery of electric power to consumers to secure the security of people’s livelihood. The methodology used in this study is both interview and questionnaire survey to analyze the response from the respondents on causes of power outages and high losses facing the electricity company of Ghana (ECG) and its effect on the livelihood on the vulnerable people. Among the outcome of both administered questionnaire and the interview survey from the field were; poor maintenance of existing sub-stations, use of aging equipment, use of poor distribution infrastructure and poor metering and billing system. The main observation of this paper is that the poor network efficiency (high losses and power outages) affects the livelihood of the vulnerable people. Therefore, the paper recommends that policymakers should insist on all regulation guiding electricity distribution to improve system efficiency. In conclusion, there should be decentralization of off-grid solar PV technologies to provide a sustainable and cost-effective, which can increase daily productivity and improve the quality of life of the vulnerable people in the rural communities.

Keywords: electricity efficiency, high losses, human security, power outage

Procedia PDF Downloads 264
247 Landslide Susceptibility Analysis in the St. Lawrence Lowlands Using High Resolution Data and Failure Plane Analysis

Authors: Kevin Potoczny, Katsuichiro Goda

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The St. Lawrence lowlands extend from Ottawa to Quebec City and are known for large deposits of sensitive Leda clay. Leda clay deposits are responsible for many large landslides, such as the 1993 Lemieux and 2010 St. Jude (4 fatalities) landslides. Due to the large extent and sensitivity of Leda clay, regional hazard analysis for landslides is an important tool in risk management. A 2018 regional study by Farzam et al. on the susceptibility of Leda clay slopes to landslide hazard uses 1 arc second topographical data. A qualitative method known as Hazus is used to estimate susceptibility by checking for various criteria in a location and determine a susceptibility rating on a scale of 0 (no susceptibility) to 10 (very high susceptibility). These criteria are slope angle, geological group, soil wetness, and distance from waterbodies. Given the flat nature of St. Lawrence lowlands, the current assessment fails to capture local slopes, such as the St. Jude site. Additionally, the data did not allow one to analyze failure planes accurately. This study majorly improves the analysis performed by Farzam et al. in two aspects. First, regional assessment with high resolution data allows for identification of local locations that may have been previously identified as low susceptibility. This then provides the opportunity to conduct a more refined analysis on the failure plane of the slope. Slopes derived from 1 arc second data are relatively gentle (0-10 degrees) across the region; however, the 1- and 2-meter resolution 2022 HRDEM provided by NRCAN shows that short, steep slopes are present. At a regional level, 1 arc second data can underestimate the susceptibility of short, steep slopes, which can be dangerous as Leda clay landslides behave retrogressively and travel upwards into flatter terrain. At the location of the St. Jude landslide, slope differences are significant. 1 arc second data shows a maximum slope of 12.80 degrees and a mean slope of 4.72 degrees, while the HRDEM data shows a maximum slope of 56.67 degrees and a mean slope of 10.72 degrees. This equates to a difference of three susceptibility levels when the soil is dry and one susceptibility level when wet. The use of GIS software is used to create a regional susceptibility map across the St. Lawrence lowlands at 1- and 2-meter resolutions. Failure planes are necessary to differentiate between small and large landslides, which have so far been ignored in regional analysis. Leda clay failures can only retrogress as far as their failure planes, so the regional analysis must be able to transition smoothly into a more robust local analysis. It is expected that slopes within the region, once previously assessed at low susceptibility scores, contain local areas of high susceptibility. The goal is to create opportunities for local failure plane analysis to be undertaken, which has not been possible before. Due to the low resolution of previous regional analyses, any slope near a waterbody could be considered hazardous. However, high-resolution regional analysis would allow for more precise determination of hazard sites.

Keywords: hazus, high-resolution DEM, leda clay, regional analysis, susceptibility

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246 Funding Innovative Activities in Firms: The Ownership Structure and Governance Linkage - Evidence from Mongolia

Authors: Ernest Nweke, Enkhtuya Bavuudorj

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The harsh realities of the scandalous failure of several notable corporations in the past two decades have inextricably resulted in a surge in corporate governance studies. Nevertheless, little or no attention has been paid to corporate governance studies in Mongolian firms and much less to the comprehension of the correlation among ownership structure, corporate governance mechanisms and trend of innovative activities. Innovation is the bed rock of enterprise success. However, the funding and support for innovative activities in many firms are to a great extent determined by the incentives provided by the firm’s internal and external governance mechanisms. Mongolia is an East Asian country currently undergoing a fast-paced transition from socialist to democratic system and it is a widely held view that private ownership as against public ownership fosters innovation. Hence, following the privatization policy of Mongolian Government which has led to the transfer of the ownership of hitherto state controlled and state directed firms to private individuals and organizations, expectations are high that sufficient motivation would be provided for firm managers to engage in innovative activities. This research focuses on the relationship between ownership structure, corporate governance on one hand and the level of innovation on the hand. The paper is empirical in nature and derives data from both reliable secondary and primary sources. Secondary data for the study was in respect of ownership structure of Mongolian listed firms and innovation trend in Mongolia generally. These were analyzed using tables, charts, bars and percentages. Personal interviews and surveys were held to collect primary data. Primary data was in respect of corporate governance practices in Mongolian firms and were collected using structured questionnaire. Out of a population of three hundred and twenty (320) companies listed on the Mongolian Stock Exchange (MSE), a sample size of thirty (30) randomly selected companies was utilized for the study. Five (5) management level employees were surveyed in each selected firm giving a total of one hundred and fifty (150) respondents. Data collected were analyzed and research hypotheses tested using Chi-Square test statistic. Research results showed that corporate governance mechanisms were better and have significantly improved overtime in privately held as opposed to publicly owned firms. Consequently, the levels of innovation in privately held firms were considerably higher. It was concluded that a significant and positive relationship exists between private ownership and good corporate governance on one hand and the level of funding provided for innovative activities in Mongolian firms on the other hand.

Keywords: corporate governance, innovation, ownership structure, stock exchange

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245 Securing Communities to Bring Sustainable Development, Building Peace and Community Safety: the Ethiopian Community Policing in Amhara National Regional State of Ethiopia

Authors: Demelash Kassaye

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The Ethiopia case study reveals a unique model of community policing that has developed from a particular political context in which there is a history of violent political transition, a political structure characterized by ethnic federalism and a political ideology that straddles liberal capitalism and democracy on the one hand, and state-led development and centralized control on the other. The police see community policing as a way to reduce crime. Communities speak about community policing as an opportunity to take on policing responsibilities themselves. Both of these objectives are brought together in an overarching rhetoric of community policing as a way of ‘mobilizing for development’ – whereby the community cooperate with the police to reduce crime, which otherwise inhibits development progress. Community policing in Amhara has primarily involved the placement of Community Police Officers at the kebele level across the State. In addition, a number of structures have also been established in the community, including Advisory Councils, Conflict Resolving Committees, family police and the use of shoe shiner’s and other trade associations as police informants. In addition to these newly created structures, community policing also draws upon pre-existing customary actors, such as militia and elders. Conflict Resolving Committees, Community Police Officers and elders were reported as the most common first ports of call when community members experience a crime. The analysis highlights that the model of community policing in Amhara increased communities’ access to policing services, although this is not always attended by increased access to justice. Community members also indicate that public perceptions of the police have improved since the introduction of community policing, in part due to individual Community Police Officers who have, with limited resources, innovated some impressive strategies to improve safety in their neighborhoods. However, more broadly, community policing has provided the state with more effective surveillance of the population – a potentially oppressive function in the current political context. Ultimately, community policing in Amhara is anything but straightforward. It has been a process of attempting to demonstrate the benefits of newfound (and controversial) ‘democracy’ following years of dictatorship, drawing on generations of customary dispute resolution, providing both improved access to security for communities and an enhanced surveillance capacity for the state. For external actors looking to engage in community policing, this case study reveals the importance of close analysis in assessing potential merits, risks and entry points of programming. Factors found to be central in shaping the nature of community policing in the Amhara case include the structure of the political system, state-society relations, cultures dispute resolution and political ideology.

Keywords: community policing, community, militias, ethiopia

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244 Modeling and Analysis Of Occupant Behavior On Heating And Air Conditioning Systems In A Higher Education And Vocational Training Building In A Mediterranean Climate

Authors: Abderrahmane Soufi

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The building sector is the largest consumer of energy in France, accounting for 44% of French consumption. To reduce energy consumption and improve energy efficiency, France implemented an energy transition law targeting 40% energy savings by 2030 in the tertiary building sector. Building simulation tools are used to predict the energy performance of buildings but the reliability of these tools is hampered by discrepancies between the real and simulated energy performance of a building. This performance gap lies in the simplified assumptions of certain factors, such as the behavior of occupants on air conditioning and heating, which is considered deterministic when setting a fixed operating schedule and a fixed interior comfort temperature. However, the behavior of occupants on air conditioning and heating is stochastic, diverse, and complex because it can be affected by many factors. Probabilistic models are an alternative to deterministic models. These models are usually derived from statistical data and express occupant behavior by assuming a probabilistic relationship to one or more variables. In the literature, logistic regression has been used to model the behavior of occupants with regard to heating and air conditioning systems by considering univariate logistic models in residential buildings; however, few studies have developed multivariate models for higher education and vocational training buildings in a Mediterranean climate. Therefore, in this study, occupant behavior on heating and air conditioning systems was modeled using logistic regression. Occupant behavior related to the turn-on heating and air conditioning systems was studied through experimental measurements collected over a period of one year (June 2023–June 2024) in three classrooms occupied by several groups of students in engineering schools and professional training. Instrumentation was provided to collect indoor temperature and indoor relative humidity in 10-min intervals. Furthermore, the state of the heating/air conditioning system (off or on) and the set point were determined. The outdoor air temperature, relative humidity, and wind speed were collected as weather data. The number of occupants, age, and sex were also considered. Logistic regression was used for modeling an occupant turning on the heating and air conditioning systems. The results yielded a proposed model that can be used in building simulation tools to predict the energy performance of teaching buildings. Based on the first months (summer and early autumn) of the investigations, the results illustrate that the occupant behavior of the air conditioning systems is affected by the indoor relative humidity and temperature in June, July, and August and by the indoor relative humidity, temperature, and number of occupants in September and October. Occupant behavior was analyzed monthly, and univariate and multivariate models were developed.

Keywords: occupant behavior, logistic regression, behavior model, mediterranean climate, air conditioning, heating

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243 Petrology of the Post-Collisional Dolerites, Basalts from the Javakheti Highland, South Georgia

Authors: Bezhan Tutberidze

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The Neogene-Quaternary volcanic rocks of the Javakheti Highland are products of post-collisional continental magmatism and are related to divergent and convergent margins of Eurasian-Afroarabian lithospheric plates. The studied area constitutes an integral part of the volcanic province of Central South Georgia. Three cycles of volcanic activity are identified here: 1. Late Miocene-Early Pliocene, 2. Late Pliocene-Early /Middle/ Pleistocene and 3. Late Pleistocene. An intense basic dolerite magmatic activity occurred within the time span of the Late Pliocene and lasted until at least Late /Middle/ Pleistocene. The age of the volcanogenic and volcanogenic-sedimentary formation was dated by geomorphological, paleomagnetic, paleontological and geochronological methods /1.7-1.9 Ma/. The volcanic area of the Javakheti Highland contains multiple dolerite Plateaus: Akhalkalaki, Gomarethi, Dmanisi, and Tsalka. Petrographic observations of these doleritic rocks reveal fairly constant mineralogical composition: olivine / Fo₈₇.₆₋₈₂.₇ /, plagioclase / Ab₂₂.₈ An₇₅.₉ Or₁.₃; Ab₄₅.₀₋₃₂.₃ An₅₂.₉₋₆₂.₃ Or₂.₁₋₅.₄/. The pyroxene is an augite and may exhibit a visible zoning: / Wo 39.7-43.1 En 43.5-45.2 Fs 16.8-11.7/. Opaque minerals /magnetite, titanomagnetite/ is abundant as inclusions within olivine and pyroxene crystals. The texture of dolerites exhibits intergranular, holocrystalline to ophitic to sub ophitic granular. Dolerites are most common vesicular rocks. Vesicles range in shape from spherical to elongated and in size from 0.5 mm to than 1.5-2 cm and makeup about 20-50 % of the volume. The dolerites have been subjected to considerable alteration. The secondary minerals in the geothermal field are: zeolite, calcite, chlorite, aragonite, clay-like mineral /dominated by smectites/ and iddingsite –like mineral; rare quartz and pumpellyite are present. These vesicles are filled by secondary minerals. In the chemistry, dolerites are the calc-alkalic transition to sub-alkaline with a predominance of Na₂O over K₂O. Chemical analyses indicate that dolerites of all plateaus of the Javakheti Highland have similar geochemical compositions, signifying that they were formed from the same magmatic source by crystallization of olivine basalis magma which less differentiated / ⁸⁷Sr \ ⁸⁶Sr 0.703920-0704195/. There is one argument, which is less convincing, according to which the dolerites/basalts of the Javakheti Highland are considered to be an activity of a mantle plume. Unfortunately, there does not exist reliable evidence to prove this. The petrochemical peculiarities and eruption nature of the dolerites of the Javakheti Plateau point against their plume origin. Nevertheless, it is not excluded that they influence the formation of dolerite producing primary basaltic magma.

Keywords: calc-alkalic, dolerite, Georgia, Javakheti Highland

Procedia PDF Downloads 245
242 Enhancement of Radiosensitization by Aptamer 5TR1-Functionalized AgNCs for Triple-Negative Breast Cancer

Authors: Xuechun Kan, Dongdong Li, Fan Li, Peidang Liu

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Triple-negative breast cancer (TNBC) is the most malignant subtype of breast cancer with a poor prognosis, and radiotherapy is one of the main treatment methods. However, due to the obvious resistance of tumor cells to radiotherapy, high dose of ionizing radiation is required during radiotherapy, which causes serious damage to normal tissues near the tumor. Therefore, how to improve radiotherapy resistance and enhance the specific killing of tumor cells by radiation is a hot issue that needs to be solved in clinic. Recent studies have shown that silver-based nanoparticles have strong radiosensitization, and silver nanoclusters (AgNCs) also provide a broad prospect for tumor targeted radiosensitization therapy due to their ultra-small size, low toxicity or non-toxicity, self-fluorescence and strong photostability. Aptamer 5TR1 is a 25-base oligonucleotide aptamer that can specifically bind to mucin-1 highly expressed on the membrane surface of TNBC 4T1 cells, and can be used as a highly efficient tumor targeting molecule. In this study, AgNCs were synthesized by DNA template based on 5TR1 aptamer (NC-T5-5TR1), and its role as a targeted radiosensitizer in TNBC radiotherapy was investigated. The optimal DNA template was first screened by fluorescence emission spectroscopy, and NC-T5-5TR1 was prepared. NC-T5-5TR1 was characterized by transmission electron microscopy, ultraviolet-visible spectroscopy and dynamic light scattering. The inhibitory effect of NC-T5-5TR1 on cell activity was evaluated using the MTT method. Laser confocal microscopy was employed to observe NC-T5-5TR1 targeting 4T1 cells and verify its self-fluorescence characteristics. The uptake of NC-T5-5TR1 by 4T1 cells was observed by dark-field imaging, and the uptake peak was evaluated by inductively coupled plasma mass spectrometry. The radiation sensitization effect of NC-T5-5TR1 was evaluated through cell cloning and in vivo anti-tumor experiments. Annexin V-FITC/PI double staining flow cytometry was utilized to detect the impact of nanomaterials combined with radiotherapy on apoptosis. The results demonstrated that the particle size of NC-T5-5TR1 is about 2 nm, and the UV-visible absorption spectrum detection verifies the successful construction of NC-T5-5TR1, and it shows good dispersion. NC-T5-5TR1 significantly inhibited the activity of 4T1 cells and effectively targeted and fluoresced within 4T1 cells. The uptake of NC-T5-5TR1 reached its peak at 3 h in the tumor area. Compared with AgNCs without aptamer modification, NC-T5-5TR1 exhibited superior radiation sensitization, and combined radiotherapy significantly inhibited the activity of 4T1 cells and tumor growth in 4T1-bearing mice. The apoptosis level of NC-T5-5TR1 combined with radiation was significantly increased. These findings provide important theoretical and experimental support for NC-T5-5TR1 as a radiation sensitizer for TNBC.

Keywords: 5TR1 aptamer, silver nanoclusters, radio sensitization, triple-negative breast cancer

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241 Social Mobility and Urbanization: Case Study of Well-Educated Urban Migrant's Life Experience in the Era of China's New Urbanization Project

Authors: Xu Heng

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Since the financial crisis of 2008 and the resulting Great Recession, the number of China’s unemployed college graduate reached over 500 thousand in 2011. Following the severe situation of college graduate employment, there has been growing public concern about college graduates, especially those with the less-privileged background, and their working and living condition in metropolises. Previous studies indicate that well-educated urban migrants with less-privileged background tend to obtain temporary occupation with less financial income and lower social status. Those vulnerable young migrants are described as ‘Ant Tribe’ by some scholars. However, since the implementation of a new urbanization project, together with the relaxed Hukou system and the acceleration of socio-economic development in middle/small cities, some researchers described well-educated urban migrant’s situation and the prospect of upward social mobility in urban areas in an overly optimistic light. In order to shed more lights on the underlying tensions encountered by China’s well-educated urban migrants in their upward social mobility pursuit, this research mainly focuses on 10 well-educated urban migrants’ life trajectories between their university-to-work transition and their current situation. All selected well-educated urban migrants are young adults with rural background who have already received higher education qualification from first-tier universities of Wuhan City (capital of Hubei Province). Drawing on the in-depth interviews with 10 participants and Inspired by Lahire’s Theory of Plural Actor, this study yields the following preliminary findings; 1) For those migrants who move to super-mega cities (i.e., Beijing, Shenzhen, Guangzhou) or stay in Wuhan after college graduation, their inadequacies of economic and social capital are the structural factors which negatively influence their living condition and further shape their plan for career development. The incompatibility between the sub-fields of urban life and the disposition, which generated from their early socialization, is the main cause for marginalized position in the metropolises. 2) For those migrants who move back to middle/small cities located in their hometown regions, the inconsistency between the disposition, which generated from college life, and the organizational habitus of the workplace is the main cause for their sense of ‘fish out of water’, even though they have obtained the stable occupation of local government or state-owned enterprise. On the whole, this research illuminates how the underlying the structural forces shape well-educated urban migrants’ life trajectories and hinder their upward social mobility under the context of new urbanization project.

Keywords: life trajectory, social mobility, urbanization, well-educated urban migrant

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240 Closing the Loop between Building Sustainability and Stakeholder Engagement: Case Study of an Australian University

Authors: Karishma Kashyap, Subha D. Parida

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Rapid population growth and urbanization is creating pressure throughout the world. This has a dramatic effect on a lot of elements which include water, food, transportation, energy, infrastructure etc. as few of the key services. Built environment sector is growing concurrently to meet the needs of urbanization. Due to such large scale development of buildings, there is a need for them to be monitored and managed efficiently. Along with appropriate management, climate adaptation is highly crucial as well because buildings are one of the major sources of greenhouse gas emission in their operation phase. Buildings to be adaptive need to provide a triple bottom approach to sustainability i.e., being socially, environmentally and economically sustainable. Hence, in order to deliver these sustainability outcomes, there is a growing understanding and thrive towards switching to green buildings or renovating new ones as per green standards wherever possible. Academic institutions in particular have been following this trend globally. This is highly significant as universities usually have high occupancy rates because they manage a large building portfolio. Also, as universities accommodate the future generation of architects, policy makers etc., they have the potential of setting themselves as a best industry practice model for research and innovation for the rest to follow. Hence their climate adaptation, sustainable growth and performance management becomes highly crucial in order to provide the best services to users. With the objective of evaluating appropriate management mechanisms within academic institutions, a feasibility study was carried out in a recent 5-Star Green Star rated university building (housing the School of Construction) in Victoria (south-eastern state of Australia). The key aim was to understand the behavioral and social aspect of the building users, management and the impact of their relationship on overall building sustainability. A survey was used to understand the building occupant’s response and reactions in terms of their work environment and management. A report was generated based on the survey results complemented with utility and performance data which were then used to evaluate the management structure of the university. Followed by the report, interviews were scheduled with the facility and asset managers in order to understand the approach they use to manage the different buildings in their university campuses (old, new, refurbished), respective building and parameters incorporated in maintaining the Green Star performance. The results aimed at closing the communication and feedback loop within the respective institutions and assist the facility managers to deliver appropriate stakeholder engagement. For the wider design community, analysis of the data highlights the applicability and significance of prioritizing key stakeholders, integrating desired engagement policies within an institution’s management structures and frameworks and their effect on building performance

Keywords: building optimization, green building, post occupancy evaluation, stakeholder engagement

Procedia PDF Downloads 340
239 Techno-Economic Analysis of 1,3-Butadiene and ε-Caprolactam Production from C6 Sugars

Authors: Iris Vural Gursel, Jonathan Moncada, Ernst Worrell, Andrea Ramirez

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In order to achieve the transition from a fossil to bio-based economy, biomass needs to replace fossil resources in meeting the world’s energy and chemical needs. This calls for development of biorefinery systems allowing cost-efficient conversion of biomass to chemicals. In biorefinery systems, feedstock is converted to key intermediates called platforms which are converted to wide range of marketable products. The C6 sugars platform stands out due to its unique versatility as precursor for multiple valuable products. Among the different potential routes from C6 sugars to bio-based chemicals, 1,3-butadiene and ε-caprolactam appear to be of great interest. Butadiene is an important chemical for the production of synthetic rubbers, while caprolactam is used in production of nylon-6. In this study, ex-ante techno-economic performance of 1,3-butadiene and ε-caprolactam routes from C6 sugars were assessed. The aim is to provide insight from an early stage of development into the potential of these new technologies, and the bottlenecks and key cost-drivers. Two cases for each product line were analyzed to take into consideration the effect of possible changes on the overall performance of both butadiene and caprolactam production. Conceptual process design for the processes was developed using Aspen Plus based on currently available data from laboratory experiments. Then, operating and capital costs were estimated and an economic assessment was carried out using Net Present Value (NPV) as indicator. Finally, sensitivity analyses on processing capacity and prices was done to take into account possible variations. Results indicate that both processes perform similarly from an energy intensity point of view ranging between 34-50 MJ per kg of main product. However, in terms of processing yield (kg of product per kg of C6 sugar), caprolactam shows higher yield by a factor 1.6-3.6 compared to butadiene. For butadiene production, with the economic parameters used in this study, for both cases studied, a negative NPV (-642 and -647 M€) was attained indicating economic infeasibility. For the caprolactam production, one of the cases also showed economic infeasibility (-229 M€), but the case with the higher caprolactam yield resulted in a positive NPV (67 M€). Sensitivity analysis indicated that the economic performance of caprolactam production can be improved with the increase in capacity (higher C6 sugars intake) reflecting benefits of the economies of scale. Furthermore, humins valorization for heat and power production was considered and found to have a positive effect. Butadiene production was found sensitive to the price of feedstock C6 sugars and product butadiene. However, even at 100% variation of the two parameters, butadiene production remained economically infeasible. Overall, the caprolactam production line shows higher economic potential in comparison to that of butadiene. The results are useful in guiding experimental research and providing direction for further development of bio-based chemicals.

Keywords: bio-based chemicals, biorefinery, C6 sugars, economic analysis, process modelling

Procedia PDF Downloads 137
238 Iron Oxide Reduction Using Solar Concentration and Carbon-Free Reducers

Authors: Bastien Sanglard, Simon Cayez, Guillaume Viau, Thomas Blon, Julian Carrey, Sébastien Lachaize

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The need to develop clean production processes is a key challenge of any industry. Steel and iron industries are particularly concerned since they emit 6.8% of global anthropogenic greenhouse gas emissions. One key step of the process is the high-temperature reduction of iron ore using coke, leading to large amounts of CO2 emissions. One route to decrease impacts is to get rid of fossil fuels by changing both the heat source and the reducer. The present work aims at investigating experimentally the possibility to use concentrated solar energy and carbon-free reducing agents. Two sets of experimentations were realized. First, in situ X-ray diffraction on pure and industrial powder of hematite was realized to study the phase evolution as a function of temperature during reduction under hydrogen and ammonia. Secondly, experiments were performed on industrial iron ore pellets, which were reduced by NH3 or H2 into a “solar furnace” composed of a controllable 1600W Xenon lamp to simulate and control the solar concentrated irradiation of a glass reactor and of a diaphragm to control light flux. Temperature and pressure were recorded during each experiment via thermocouples and pressure sensors. The percentage of iron oxide converted to iron (called thereafter “reduction ratio”) was found through Rietveld refinement. The power of the light source and the reduction time were varied. Results obtained in the diffractometer reaction chamber show that iron begins to form at 300°C with pure Fe2O3 powder and 400°C with industrial iron ore when maintained at this temperature for 60 minutes and 80 minutes, respectively. Magnetite and wuestite are detected on both powders during the reduction under hydrogen; under ammonia, iron nitride is also detected for temperatures between400°C and 600°C. All the iron oxide was converted to iron for a reaction of 60 min at 500°C, whereas a conversion ratio of 96% was reached with industrial powder for a reaction of 240 min at 600°C under hydrogen. Under ammonia, full conversion was also reached after 240 min of reduction at 600 °C. For experimentations into the solar furnace with iron ore pellets, the lamp power and the shutter opening were varied. An 83.2% conversion ratio was obtained with a light power of 67 W/cm2 without turning over the pellets. Nevertheless, under the same conditions, turning over the pellets in the middle of the experiment permits to reach a conversion ratio of 86.4%. A reduction ratio of 95% was reached with an exposure of 16 min by turning over pellets at half time with a flux of 169W/cm2. Similar or slightly better results were obtained under an ammonia reducing atmosphere. Under the same flux, the highest reduction yield of 97.3% was obtained under ammonia after 28 minutes of exposure. The chemical reaction itself, including the solar heat source, does not produce any greenhouse gases, so solar metallurgy represents a serious way to reduce greenhouse gas emission of metallurgy industry. Nevertheless, the ecological impact of the reducers must be investigated, which will be done in future work.

Keywords: solar concentration, metallurgy, ammonia, hydrogen, sustainability

Procedia PDF Downloads 120
237 The Budget Impact of the DISCERN™ Diagnostic Test for Alzheimer’s Disease in the United States

Authors: Frederick Huie, Lauren Fusfeld, William Burchenal, Scott Howell, Alyssa McVey, Thomas F. Goss

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Alzheimer’s Disease (AD) is a degenerative brain disease characterized by memory loss and cognitive decline that presents a substantial economic burden for patients and health insurers in the US. This study evaluates the payer budget impact of the DISCERN™ test in the diagnosis and management of patients with symptoms of dementia evaluated for AD. DISCERN™ comprises three assays that assess critical factors related to AD that regulate memory, formation of synaptic connections among neurons, and levels of amyloid plaques and neurofibrillary tangles in the brain and can provide a quicker, more accurate diagnosis than tests in the current diagnostic pathway (CDP). An Excel-based model with a three-year horizon was developed to assess the budget impact of DISCERN™ compared with CDP in a Medicare Advantage plan with 1M beneficiaries. Model parameters were identified through a literature review and were verified through consultation with clinicians experienced in diagnosis and management of AD. The model assesses direct medical costs/savings for patients based on the following categories: •Diagnosis: costs of diagnosis using DISCERN™ and CDP. •False Negative (FN) diagnosis: incremental cost of care avoidable with a correct AD diagnosis and appropriately directed medication. •True Positive (TP) diagnosis: AD medication costs; cost from a later TP diagnosis with the CDP versus DISCERN™ in the year of diagnosis, and savings from the delay in AD progression due to appropriate AD medication in patients who are correctly diagnosed after a FN diagnosis.•False Positive (FP) diagnosis: cost of AD medication for patients who do not have AD. A one-way sensitivity analysis was conducted to assess the effect of varying key clinical and cost parameters ±10%. An additional scenario analysis was developed to evaluate the impact of individual inputs. In the base scenario, DISCERN™ is estimated to decrease costs by $4.75M over three years, equating to approximately $63.11 saved per test per year for a cohort followed over three years. While the diagnosis cost is higher with DISCERN™ than with CDP modalities, this cost is offset by the higher overall costs associated with CDP due to the longer time needed to receive a TP diagnosis and the larger number of patients who receive a FN diagnosis and progress more rapidly than if they had received appropriate AD medication. The sensitivity analysis shows that the three parameters with the greatest impact on savings are: reduced sensitivity of DISCERN™, improved sensitivity of the CDP, and a reduction in the percentage of disease progression that is avoided with appropriate AD medication. A scenario analysis in which DISCERN™ reduces the utilization for patients of computed tomography from 21% in the base case to 16%, magnetic resonance imaging from 37% to 27% and cerebrospinal fluid biomarker testing, positive emission tomography, electroencephalograms, and polysomnography testing from 4%, 5%, 10%, and 8%, respectively, in the base case to 0%, results in an overall three-year net savings of $14.5M. DISCERN™ improves the rate of accurate, definitive diagnosis of AD earlier in the disease and may generate savings for Medicare Advantage plans.

Keywords: Alzheimer’s disease, budget, dementia, diagnosis.

Procedia PDF Downloads 125
236 The Display of Environmental Information to Promote Energy Saving Practices: Evidence from a Massive Behavioral Platform

Authors: T. Lazzarini, M. Imbiki, P. E. Sutter, G. Borragan

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While several strategies, such as the development of more efficient appliances, the financing of insulation programs or the rolling out of smart meters represent promising tools to reduce future energy consumption, their implementation relies on people’s decisions-actions. Likewise, engaging with consumers to reshape their behavior has shown to be another important way to reduce energy usage. For these reasons, integrating the human factor in the energy transition has become a major objective for researchers and policymakers. Digital education programs based on tangible and gamified user interfaces have become a new tool with potential effects to reduce energy consumption4. The B2020 program, developed by the firm “Économie d’Énergie SAS”, proposes a digital platform to encourage pro-environmental behavior change among employees and citizens. The platform integrates 160 eco-behaviors to help saving energy and water and reducing waste and CO2 emissions. A total of 13,146 citizens have used the tool so far to declare the range of eco-behaviors they adopt in their daily lives. The present work seeks to build on this database to identify the potential impact of adopted energy-saving behaviors (n=62) to reduce the use of energy in buildings. To this end, behaviors were classified into three categories regarding the nature of its implementation (Eco-habits: e.g., turning-off the light, Eco-actions: e.g., installing low carbon technology such as led light-bulbs and Home-Refurbishments: e.g., such as wall-insulation or double-glazed energy efficient windows). General Linear Models (GLM) disclosed the existence of a significantly higher frequency of Eco-habits when compared to the number of home-refurbishments realized by the platform users. While this might be explained in part by the high financial costs that are associated with home renovation works, it also contrasts with the up to three times larger energy-savings that can be accomplished by these means. Furthermore, multiple regression models failed to disclose the expected relationship between energy-savings and frequency of adopted eco behaviors, suggesting that energy-related practices are not necessarily driven by the correspondent energy-savings. Finally, our results also suggested that people adopting more Eco-habits and Eco-actions were more likely to engage in Home-Refurbishments. Altogether, these results fit well with a growing body of scientific research, showing that energy-related practices do not necessarily maximize utility, as postulated by traditional economic models, and suggest that other variables might be triggering them. Promoting home refurbishments could benefit from the adoption of complementary energy-saving habits and actions.

Keywords: energy-saving behavior, human performance, behavioral change, energy efficiency

Procedia PDF Downloads 176
235 Hydrogen Production from Auto-Thermal Reforming of Ethanol Catalyzed by Tri-Metallic Catalyst

Authors: Patrizia Frontera, Anastasia Macario, Sebastiano Candamano, Fortunato Crea, Pierluigi Antonucci

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The increasing of the world energy demand makes today biomass an attractive energy source, based on the minimizing of CO2 emission and on the global warming reduction purposes. Recently, COP-21, the international meeting on global climate change, defined the roadmap for sustainable worldwide development, based on low-carbon containing fuel. Hydrogen is an energy vector able to substitute the conventional fuels from petroleum. Ethanol for hydrogen production represents a valid alternative to the fossil sources due to its low toxicity, low production costs, high biodegradability, high H2 content and renewability. Ethanol conversion to generate hydrogen by a combination of partial oxidation and steam reforming reactions is generally called auto-thermal reforming (ATR). The ATR process is advantageous due to the low energy requirements and to the reduced carbonaceous deposits formation. Catalyst plays a pivotal role in the ATR process, especially towards the process selectivity and the carbonaceous deposits formation. Bimetallic or trimetallic catalysts, as well as catalysts with doped-promoters supports, may exhibit high activity, selectivity and deactivation resistance with respect to the corresponding monometallic ones. In this work, NiMoCo/GDC, NiMoCu/GDC and NiMoRe/GDC (where GDC is Gadolinia Doped Ceria support and the metal composition is 60:30:10 for all catalyst) have been prepared by impregnation method. The support, Gadolinia 0.2 Doped Ceria 0.8, was impregnated by metal precursors solubilized in aqueous ethanol solution (50%) at room temperature for 6 hours. After this, the catalysts were dried at 100°C for 8 hours and, subsequently, calcined at 600°C in order to have the metal oxides. Finally, active catalysts were obtained by reduction procedure (H2 atmosphere at 500°C for 6 hours). All sample were characterized by different analytical techniques (XRD, SEM-EDX, XPS, CHNS, H2-TPR and Raman Spectorscopy). Catalytic experiments (auto-thermal reforming of ethanol) were carried out in the temperature range 500-800°C under atmospheric pressure, using a continuous fixed-bed microreactor. Effluent gases from the reactor were analyzed by two Varian CP4900 chromarographs with a TCD detector. The analytical investigation focused on the preventing of the coke deposition, the metals sintering effect and the sulfur poisoning. Hydrogen productivity, ethanol conversion and products distribution were measured and analyzed. At 600°C, all tri-metallic catalysts show the best performance: H2 + CO reaching almost the 77 vol.% in the final gases. While NiMoCo/GDC catalyst shows the best selectivity to hydrogen whit respect to the other tri-metallic catalysts (41 vol.% at 600°C). On the other hand, NiMoCu/GDC and NiMoRe/GDC demonstrated high sulfur poisoning resistance (up to 200 cc/min) with respect to the NiMoCo/GDC catalyst. The correlation among catalytic results and surface properties of the catalysts will be discussed.

Keywords: catalysts, ceria, ethanol, gadolinia, hydrogen, Nickel

Procedia PDF Downloads 139
234 Prominent Lipid Parameters Correlated with Trunk-to-Leg and Appendicular Fat Ratios in Severe Pediatric Obesity

Authors: Mustafa M. Donma, Orkide Donma

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The examination of both serum lipid fractions and body’s lipid composition are quite informative during the evaluation of obesity stages. Within this context, alterations in lipid parameters are commonly observed. The variations in the fat distribution of the body are also noteworthy. Total cholesterol (TC), triglycerides (TRG), low density lipoprotein-cholesterol (LDL-C), high density lipoprotein-cholesterol (HDL-C) are considered as the basic lipid fractions. Fat deposited in trunk and extremities may give considerable amount of information and different messages during discrete health states. Ratios are also derived from distinct fat distribution in these areas. Trunk-to-leg fat ratio (TLFR) and trunk-to-appendicular fat ratio (TAFR) are the most recently introduced ratios. In this study, lipid fractions and TLFR, as well as TAFR, were evaluated, and the distinctions among healthy, obese (OB), and morbid obese (MO) groups were investigated. Three groups [normal body mass index (N-BMI), OB, MO] were constituted from a population aged 6 to 18 years. Ages and sexes of the groups were matched. The study protocol was approved by the Non-interventional Ethics Committee of Tekirdag Namik Kemal University. Written informed consent forms were obtained from the parents of the participants. Anthropometric measurements (height, weight, waist circumference, hip circumference, head circumference, neck circumference) were obtained and recorded during the physical examination. Body mass index values were calculated. Total, trunk, leg, and arm fat mass values were obtained by TANITA Bioelectrical Impedance Analysis. These values were used to calculate TLFR and TAFR. Systolic (SBP) and diastolic blood pressures (DBP) were measured. Routine biochemical tests including TC, TRG, LDL-C, HDL-C, and insulin were performed. Data were evaluated using SPSS software. p value smaller than 0.05 was accepted as statistically significant. There was no difference among the age values and gender ratios of the groups. Any statistically significant difference was not observed in terms of DBP, TLFR as well as serum lipid fractions. Higher SBP values were measured both in OB and MO children than those with N-BMI. TAFR showed a significant difference between N-BMI and OB groups. Statistically significant increases were detected between insulin values of N-BMI group and OB as well as MO groups. There were bivariate correlations between LDL and TLFR (r=0.396; p=0.037) as well as TAFR values (r=0.413; p=0.029) in MO group. When adjusted for SBP and DBP, partial correlations were calculated as (r=0.421; p=0.032) and (r=0.438; p=0.025) for LDL-TLFR as well as LDL-TAFR, respectively. Much stronger partial correlations were obtained for the same couples (r=0.475; p=0.019 and r=0.473; p=0.020, respectively) upon controlling for TRG and HDL-C. Much stronger partial correlations observed in MO children emphasize the potential transition from morbid obesity to metabolic syndrome. These findings have concluded that LDL-C may be suggested as a discriminating parameter between OB and MO children.

Keywords: children, lipid parameters, obesity, trunk-to-leg fat ratio, trunk-to-appendicular fat ratio

Procedia PDF Downloads 96
233 State Violence: The Brazilian Amnesty Law and the Fight Against Impunity

Authors: Flavia Kroetz

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From 1964 to 1985, Brazil was ruled by a dictatorial regime that, under the discourse of fight against terrorism and subversion, implemented cruel and atrocious practices against anyone who opposed the State ideology. At the same time, several Latin American countries faced dictatorial periods and experienced State repression through apparatuses of violence institutionalized in the very governmental structure. Despite the correspondence between repressive methods adopted by authoritarian regimes in States such as Argentina, Chile, El Salvador, Peru and Uruguay, the mechanisms of democratic transition adopted with the end of each dictatorship were significantly different. While some States have found ways to deal with past atrocities through serious and transparent investigations of the crimes perpetrated in the name of repression, in others, as in Brazil, a culture of impunity remains rooted in society, manifesting itself in the widespread disbelief of the population in governmental and democratic institutions. While Argentina, Chile, Peru and Uruguay are convincing examples of the possibility and importance of the prosecution of crimes such as torture, forced disappearance and murder committed by the State, El Salvador demonstrates the complete failure to punish or at least remove from power the perpetrators of serious crimes against civilians and political opponents. In a scenario of widespread violations of human rights, State violence becomes entrenched within society as a daily and even necessary practice. In Brazil, a lack of political and judicial will withstands the impunity of those who, during the military regime, committed serious crimes against human rights under the authority of the State. If the reproduction of violence is a direct consequence of the culture of denial and the rejection of everyone considered to be different, ‘the other’, then the adoption of transitional mechanisms that underpin the historical and political contexts of the time seems essential. Such mechanisms must strengthen democracy through the effective implementation of the rights to memory and to truth, the right to justice and reparations for victims and their families, as well as institutional changes in order to remove from power those who, when in power, could not distinguish between legality and authoritarianism. Against this background, this research analyses the importance of transitional justice for the restoration of democracy, considering the adoption of amnesty laws as a strategy to preclude criminal prosecution of offenses committed during dictatorial regimes. The study investigates the scope of Law No 6.683/79, the Brazilian amnesty law, which, according to a 2010 decision of the Brazilian Constitutional Supreme Court, granted amnesty to those responsible for political crimes and related crimes, committed between September 2, 1961 and August 15, 1979. Was the purpose of this Law to grant amnesty to violent crimes committed by the State? If so, is it possible to recognize the legitimacy of a Congress composed of indirectly elected politicians controlled by the dictatorship?

Keywords: amnesty law, criminal justice, dictatorship, state violence

Procedia PDF Downloads 427
232 Anti-DNA Antibodies from Patients with Schizophrenia Hydrolyze DNA

Authors: Evgeny A. Ermakov, Lyudmila P. Smirnova, Valentina N. Buneva

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Schizophrenia associated with dysregulation of neurotransmitter processes in the central nervous system and disturbances in the humoral immune system resulting in the formation of antibodies (Abs) to the various components of the nervous tissue. Abs to different neuronal receptors and DNA were detected in the blood of patients with schizophrenia. Abs hydrolyzing DNA were detected in pool of polyclonal autoantibodies in autoimmune and infectious diseases, such catalytic Abs were named abzymes. It is believed that DNA-hydrolyzing abzymes are cytotoxic, cause nuclear DNA fragmentation and induce cell death by apoptosis. Abzymes with DNAase activity are interesting because of the mechanism of formation and the possibility of use as diagnostic markers. Therefore, in our work we have set following goals: to determine the level anti-DNA Abs in the serum of patients with schizophrenia and to study DNA-hydrolyzing activity of IgG of patients with schizophrenia. Materials and methods: In our study there were included 41 patients with a verified diagnosis of paranoid or simple schizophrenia and 24 healthy donors. Electrophoretically and immunologically homogeneous IgGs were obtained by sequential affinity chromatography of the serum proteins on protein G-Sepharose and gel filtration. The levels of anti-DNA Abs were determined using ELISA. DNA-hydrolyzing activity was detected as the level of supercoiled pBluescript DNA transition in circular and linear forms, the hydrolysis products were analyzed by agarose electrophoresis followed by ethidium bromide stain. To correspond the registered catalytic activity directly to the antibodies we carried out a number of strict criteria: electrophoretic homogeneity of the antibodies, gel filtration (acid shock analysis) and in situ activity. Statistical analysis was performed in ‘Statistica 9.0’ using the non-parametric Mann-Whitney test. Results: The sera of approximately 30% of schizophrenia patients displayed a higher level of Abs interacting with single-stranded (ssDNA) and double-stranded DNA (dsDNA) compared with healthy donors. The average level of Abs interacting with ssDNA was only 1.1-fold lower than that for interacting with dsDNA. IgG of patient with schizophrenia were shown to possess DNA hydrolyzing activity. Using affinity chromatography, electrophoretic analysis of isolated IgG homogeneity, gel filtration in acid shock conditions and in situ DNAse activity analysis we proved that the observed activity is intrinsic property of studied antibodies. We have shown that the relative DNAase activity of IgG in patients with schizophrenia averaged 55.4±32.5%, IgG of healthy donors showed much lower activity (average of 9.1±6.5%). It should be noted that DNAase activity of IgG in patients with schizophrenia with a negative symptoms was significantly higher (73.3±23.8%), than in patients with positive symptoms (43.3±33.1%). Conclusion: Anti-DNA Abs of patients with schizophrenia not only bind DNA, but quite efficiently hydrolyze the substrate. The data show a correlation with the level of DNase activity and leading symptoms of patients with schizophrenia.

Keywords: anti-DNA antibodies, abzymes, DNA hydrolysis, schizophrenia

Procedia PDF Downloads 308
231 Reconstruction of Signal in Plastic Scintillator of PET Using Tikhonov Regularization

Authors: L. Raczynski, P. Moskal, P. Kowalski, W. Wislicki, T. Bednarski, P. Bialas, E. Czerwinski, A. Gajos, L. Kaplon, A. Kochanowski, G. Korcyl, J. Kowal, T. Kozik, W. Krzemien, E. Kubicz, Sz. Niedzwiecki, M. Palka, Z. Rudy, O. Rundel, P. Salabura, N.G. Sharma, M. Silarski, A. Slomski, J. Smyrski, A. Strzelecki, A. Wieczorek, M. Zielinski, N. Zon

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The J-PET scanner, which allows for single bed imaging of the whole human body, is currently under development at the Jagiellonian University. The J-PET detector improves the TOF resolution due to the use of fast plastic scintillators. Since registration of the waveform of signals with duration times of few nanoseconds is not feasible, a novel front-end electronics allowing for sampling in a voltage domain at four thresholds was developed. To take fully advantage of these fast signals a novel scheme of recovery of the waveform of the signal, based on ideas from the Tikhonov regularization (TR) and Compressive Sensing methods, is presented. The prior distribution of sparse representation is evaluated based on the linear transformation of the training set of waveform of the signals by using the Principal Component Analysis (PCA) decomposition. Beside the advantage of including the additional information from training signals, a further benefit of the TR approach is that the problem of signal recovery has an optimal solution which can be determined explicitly. Moreover, from the Bayes theory the properties of regularized solution, especially its covariance matrix, may be easily derived. This step is crucial to introduce and prove the formula for calculations of the signal recovery error. It has been proven that an average recovery error is approximately inversely proportional to the number of samples at voltage levels. The method is tested using signals registered by means of the single detection module of the J-PET detector built out from the 30 cm long BC-420 plastic scintillator strip. It is demonstrated that the experimental and theoretical functions describing the recovery errors in the J-PET scenario are largely consistent. The specificity and limitations of the signal recovery method in this application are discussed. It is shown that the PCA basis offers high level of information compression and an accurate recovery with just eight samples, from four voltage levels, for each signal waveform. Moreover, it is demonstrated that using the recovered waveform of the signals, instead of samples at four voltage levels alone, improves the spatial resolution of the hit position reconstruction. The experiment shows that spatial resolution evaluated based on information from four voltage levels, without a recovery of the waveform of the signal, is equal to 1.05 cm. After the application of an information from four voltage levels to the recovery of the signal waveform, the spatial resolution is improved to 0.94 cm. Moreover, the obtained result is only slightly worse than the one evaluated using the original raw-signal. The spatial resolution calculated under these conditions is equal to 0.93 cm. It is very important information since, limiting the number of threshold levels in the electronic devices to four, leads to significant reduction of the overall cost of the scanner. The developed recovery scheme is general and may be incorporated in any other investigation where a prior knowledge about the signals of interest may be utilized.

Keywords: plastic scintillators, positron emission tomography, statistical analysis, tikhonov regularization

Procedia PDF Downloads 426
230 Re-Orienting Fashion: Fashionable Modern Muslim Women beyond Western Modernity

Authors: Amany Abdelrazek

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Fashion is considered the main feature of modern and postmodern capitalist and consumerist society. Consumer historians maintain that fashion, namely, a sector of people embracing a prevailing clothing style for a short period, started during the Middle Ages but gained popularity later. It symbolised the transition from a medieval society with its solid fixed religious values into a modern society with its secular consumer dynamic culture. Renaissance society was a modern secular society concerning its preoccupation with daily life and changing circumstances. Yet, the late 18th-century industrial revolution revolutionised thought and ideology in Europe. The Industrial Revolution reinforced the Western belief in rationality and strengthened the position of science. In such a rational Western society, modernity, with its new ideas, came to challenge the whole idea of old fixed norms, reflecting the modern secular, rational culture and renouncing the medieval pious consumer. In modern society, supported by the industrial revolution and mass production, fashion encouraged broader sectors of society to integrate into fashion reserved for the aristocracy and royal courts. Moreover, the fashion project emphasizes the human body and its beauty, contradicting Judeo-Christian culture, which tends to abhor and criticize interest in sensuality and hedonism. In mainstream Western discourse, fashionable dress differentiates between emancipated stylish consumerist secular modern female and the assumed oppressed traditional modest religious female. Opposing this discourse, I look at the controversy over what has been called "Islamic fashion" that started during the 1980s and continued to gain popularity in contemporary Egyptian society. I discuss the challenges of being a fashionable and Muslim practicing female in light of two prominent models for female "Islamic fashion" in postcolonial Egypt; Jasmin Mohshen, the first hijabi model in Egypt and Manal Rostom, the first Muslim woman to represent the Nike campaign in the Middle East. The research employs fashion and postcolonial theories to rethink current Muslim women's position on women's emancipation, Western modernity and practising faith in postcolonial Egypt. The paper argues that Muslim women's current innovative and fashionable dress can work as a counter-discourse to the Orientalist and exclusive representation of non-Western Muslim culture as an inherently inert timeless culture. Furthermore, "Islamic" fashionable dress as an aesthetic medium for expressing ideas and convictions in contemporary Egypt interrogates the claim of universal secular modernity and Western fashion theorists' reluctance to consider Islamic fashion as fashion.

Keywords: fashion, muslim women, modernity, secularism

Procedia PDF Downloads 110
229 Conditions That Brought Bounce-Back in Southern Europe: An Inter-Temporal and Cross-National Analysis on Female Labour Force Participation with Fuzzy Set Qualitative Comparative Analysis

Authors: A. Onur Kutlu, H. Tolga Bolukbasi

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Since the 1990s, governments, international organizations and scholars have drawn increasing attention to the significance of women in the labour force. While advanced industrial countries in North Western Europe and North America have managed to increase female labour force participation (FLFP) in the early post world war two period, emerging economies of the 1970s have only been able to increase FLFP only a decade later. Among these areas, Southern Europe features a wave of remarkable bounce backs in FLFP. However, despite striking similarities between the features in Southern Europe and those in Turkey, Turkey has not been able to pull women into the labour force. Despite a host of institutional similarities, Turkey has failed to reach to the level of her Southern European neighbours. This paper addresses the puzzle why Turkey lag behind in FLFP in comparison to her Southern European neighbours. There are signs showing that FLFP is currently reaching a critical threshold at a time when structural factors may allow a trend. It is not known, however, the constellation of conditions which may bring rising FLFP in Turkey. In order to gain analytical leverage from similar transitions in countries that share similar labour market and welfare state regime characteristics, this paper identifies the conditions in Southern Europe that brought rising FLFP to be able to explore the prospects for Turkey. Second, this paper takes these variables in the fuzzy set Qualitative Comparative Analysis (fsQCA) as conditions which can potentially explain the outcome of rising FLFP in Portugal, Spain, Italy, Greece and Turkey. The purpose here is to identify any causal pathway there may exist that lead to rising FLFP in Southern Europe. In order to do so, this study analyses two time periods in all cases, which represent different periods for different countries. The first period is identified on the basis of low FLFP and the second period on the basis of the transition to significantly higher FLFP. Third, the conditions are treated following the standard procedures in fsQCA, which provide equifinal: two distinct paths to higher levels of FLFP in Southern Europe, each of which may potentially increase FLFP in Turkey. Based on this analysis, this paper proposes that there exist two distinct paths leading to higher levels of FLFP in Southern Europe. Among these paths, salience of left parties emerges as a sufficient condition. In cases where this condition was not present, a second path combining enlarging service sector employment, increased tertiary education among women and increased childcare enrolment rates led to increasing FLFP.

Keywords: female labour force participation, fsQCA, Southern Europe, Turkey

Procedia PDF Downloads 301
228 Environmental Impact of Pallets in the Supply Chain: Including Logistics and Material Durability in a Life Cycle Assessment Approach

Authors: Joana Almeida, Kendall Reid, Jonas Bengtsson

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Pallets are devices that are used for moving and storing freight and are nearly omnipresent in supply chains. The market is dominated by timber pallets, with plastic being a common alternative. Either option underpins the use of important resources (oil, land, timber), the emission of greenhouse gases and additional waste generation in most supply chains. This study uses a dynamic approach to the life cycle assessment (LCA) of pallets. It demonstrates that what ultimately defines the environmental burden of pallets in the supply chain is how often the length of its lifespan, which depends on the durability of the material and on how pallets are utilized. This study proposes a life cycle assessment (LCA) of pallets in supply chains supported by an algorithm that estimates pallet durability in function of material resilience and of logistics. The LCA runs from cradle-to-grave, including raw material provision, manufacture, transport and end of life. The scope is representative of timber and plastic pallets in the Australian and South-East Asia markets. The materials included in this analysis are: -tropical mixed hardwood, unsustainably harvested in SE Asia; -certified softwood, sustainably harvested; -conventional plastic, a mix of virgin and scrap plastic; -recycled plastic pallets, 100% mixed plastic scrap, which are being pioneered by Re > Pal. The logistical model purports that more complex supply chains and rougher handling subject pallets to higher stress loads. More stress shortens the lifespan of pallets in function of their composition. Timber pallets can be repaired, extending their lifespan, while plastic pallets cannot. At the factory gate, softwood pallets have the lowest carbon footprint. Re > pal follows closely due to its burden-free feedstock. Tropical mixed hardwood and plastic pallets have the highest footprints. Harvesting tropical mixed hardwood in SE Asia often leads to deforestation, leading to emissions from land use change. The higher footprint of plastic pallets is due to the production of virgin plastic. Our findings show that manufacture alone does not determine the sustainability of pallets. Even though certified softwood pallets have lower carbon footprint and their lifespan can be extended by repair, the need for re-supply of materials and disposal of waste timber offsets this advantage. It also leads to most waste being generated among all pallets. In a supply chain context, Re > Pal pallets have the lowest footprint due to lower replacement and disposal needs. In addition, Re > Pal are nearly ‘waste neutral’, because the waste that is generated throughout their life cycle is almost totally offset by the scrap uptake for production. The absolute results of this study can be confirmed by progressing the logistics model, improving data quality, expanding the range of materials and utilization practices. Still, this LCA demonstrates that considering logistics, raw materials and material durability is central for sustainable decision-making on pallet purchasing, management and disposal.

Keywords: carbon footprint, life cycle assessment, recycled plastic, waste

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227 Post Covid-19 Scenario and Contemporary International Security Challenges

Authors: Rubina Waseem

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The research focuses on the major crises and major effects, largely unforeseen, to counter international security concerns. At the close of 2019, the Covid-19 pandemic broke out in the city of Wuhan in Hubei province, China. The coronavirus was initially seen as an inchoate danger, aimed at striking people randomly. Owing to the extraordinary transmissibility of the virus and the highly knitted nature of the international political world, the Covid-19 soon became a formidable global challenge. The once hustling and bustling avenues, city centers, and market places became deserted. Lockdown, self-isolation, hygiene and safety, social-distancing, and job losses became a new norm. The national economies gradually plunged into crisis. The pandemic has so far caused over 33 million cases and one million deaths. The virus continues to devastate social life, as there is yet no therapeutic available. While the world was preoccupied addressing the human and social toll, the pandemic has exacerbated despair, mistrust, and friction in international relations, diplomacy, and strategy. The research will discuss how the coronavirus has accelerated the trends of transition in the postwar security order constructed by the United States. China, Russia, European Union, and other lesser regional players are now increasingly changing their security orientations to undermine the United States standing and authority in world politics. The systemic level analyses will be adopted as a methodology to broaden the lens of the study, and the research will analyze the prevalent global power distribution, whether vulnerable or exposed. The trends of parochial nationalism and isolationism are increasingly replacing multilateralism and collectivism. Yet worse, military posturing is assuming a greater role in international interactions. Taken together, the pandemic has worsened the prospects of international peace and stability by mounting equal pressure across the channels of international relations, diplomacy, and strategy. It is yet unclear which country or collectivity will face the real brunt. Despite this jaded and pessimistic view, the lingering pandemic has the potential to reinforce cooperation, multilateralism, and collectivism in the realm of international politics. There is a renewed momentum for global efforts against the pandemic. States and societies are coming closer to act as a whole. Equally important, the world leaders are feeling tempted to revisit the traditional conception of national security. In this regard, they are exploring the possibility of according preference to non-traditional security issues. In essence, the research concludes that Covid-19 has put the international political system under a great trial.

Keywords: covid-19, global challenges, international politics, international security

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226 Support for Refugee Entrepreneurs Through International Aid

Authors: Julien Benomar

Abstract:

The World Bank report published in April 2023 called “Migrants, Refugees and Society” allows us to first distinguish migrants in search of economic opportunities and refugees that flee a situation of danger and choose their destination based on their immediate need for safety. Amongst those two categories, the report distinguished people having professional skills adapted to the labor market of the host country and those who have not. Out of that distinction of four categories, we choose to focus our research on refugees that do not have professional skills adapted to the labor market of the host country. Given that refugees generally have no recourse to public assistance schemes and cannot count on the support of their entourage or support network, we propose to examine the extent to which external assistance, such as international humanitarian action, is likely to accompany refugees' transition to financial empowerment through entrepreneurship. To this end, we propose to carry out a case study structured in three stages: (i) an exchange with a Non-Governmental Organisation (NGO) active in supporting refugee populations from Congo and Burundi to Rwanda, enabling us to (i.i) define together a financial empowerment income, and (i. ii) learn about the content of the support measures taken for the beneficiaries of the humanitarian project; (ii) monitor the population of 118 beneficiaries, including 73 refugees and 45 Rwandans (reference population); (iii) conduct a participatory analysis to identify the level of performance of the project and areas for improvement. The case study thus involved the staff of an international NGO active in helping refugees from Rwanda since 2015 and the staff of a Luxembourg NGO that has been funding this economic aid project through entrepreneurship since 2021. The case study thus involved the staff of an international NGO active in helping refugees from Rwanda since 2015 and the staff of a Luxembourg NGO, which has been funding this economic aid through an entrepreneurship project since 2021, and took place over a 48-day period between April and May 2023. The main results are of two types: (i) the need to associate indicators for monitoring the impact of the project on the indirect beneficiaries of the project (refugee community) and (ii) the identification of success factors making it possible to bring concrete and relevant responses to the constraints encountered. The first result thus made it possible to identify the following indicators: Indicator of community potential ((jobs, training or mentoring) promoted by the activity of the entrepreneur), Indicator of social contribution (tax paid by the entrepreneur), Indicator of resilience (savings and loan capacity generated, and finally impact on social cohesion. The second result made it possible to identify that among the 7 success factors tested, the sector of activity chosen and the level of experience in the sector of the future activity are those that stand out the most clearly.

Keywords: entrepreuneurship, refugees, financial empowerment, international aid

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225 Characterization of Alloyed Grey Cast Iron Quenched and Tempered for a Smooth Roll Application

Authors: Mohamed Habireche, Nacer E. Bacha, Mohamed Djeghdjough

Abstract:

In the brick industry, smooth double roll crusher is used for medium and fine crushing of soft to medium hard material. Due to opposite inward rotation of the rolls, the feed material is nipped between the rolls and crushed by compression. They are subject to intense wear, known as three-body abrasion, due to the action of abrasive products. The production downtime affecting productivity stems from two sources: the bi-monthly rectification of the roll crushers and their replacement when they are completely worn out. Choosing the right material for the roll crushers should result in longer machine cycles, and reduced repair and maintenance costs. All roll crushers are imported from outside Algeria. This results in sometimes very long delivery times which handicap the brickyards, in particular in respecting delivery times and honored the orders made by customers. The aim of this work is to investigate the effect of alloying additions on microstructure and wear behavior of grey lamellar cast iron for smooth roll crushers in brick industry. The base gray iron was melted in an induction furnace with low frequency at a temperature of 1500 °C, in which return cast iron scrap, new cast iron ingot, and steel scrap were added to the melt to generate the desired composition. The chemical analysis of the bar samples was carried out using Emission Spectrometer Systems PV 8050 Series (Philips) except for the carbon, for which a carbon/sulphur analyser Elementrac CS-i was used. Unetched microstructure was used to evaluate the graphite flake morphology using the image comparison measurement method. At least five different fields were selected for quantitative estimation of phase constituents. The samples were observed under X100 magnification with a Zeiss Axiover T40 MAT optical microscope equipped with a digital camera. SEM microscope equipped with EDS was used to characterize the phases present in the microstructure. The hardness (750 kg load, 5mm diameter ball) was measured with a Brinell testing machine for both treated and as-solidified condition test pieces. The test bars were used for tensile strength and metallographic evaluations. Mechanical properties were evaluated using tensile specimens made as per ASTM E8 standards. Two specimens were tested for each alloy. From each rod, a test piece was made for the tensile test. The results showed that the quenched and tempered alloys had best wear resistance at 400 °C for alloyed grey cast iron (containing 0.62%Mn, 0.68%Cr, and 1.09% Cu) due to fine carbides in the tempered matrix. In quenched and tempered condition, increasing Cu content in cast irons improved its wear resistance moderately. Combined addition of Cu and Cr increases hardness and wear resistance for a quenched and tempered hypoeutectic grey cast iron.

Keywords: casting, cast iron, microstructure, heat treating

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224 MXene Mediated Layered 2D-3D-2D g-C3N4@WO3@Ti3C2 Multijunctional Heterostructure with Enhanced Photoelectrochemical and Photocatalytic Properties

Authors: Lekgowa Collen Makola, Cecil Naphtaly Moro Ouma, Sharon Moeno, Langelihle Dlamini

Abstract:

In recent years, advancement in the field of nanotechnology has evolved new strategies to address energy and environmental issues. Amongst the developing technologies, visible-light-driven photocatalysis is regarded as a sustainable approach for energy production and environmental detoxifications, where transition metal oxides (TMOs) and metal-free carbon-based semiconductors such as graphitic carbon nitride (CN) evidenced notable potential in this matter. Herein, g-C₃N₄@WO₃@Ti₃C₂Tx three-component multijunction photocatalyst was fabricated via facile ultrasonic-assisted self-assembly, followed by calcination to facilitate extensive integrations of the materials. A series of different Ti₃C₂ wt% loading in the g-C₃N4@WO₃@Ti₃C₂Tx were prepared and represented as 1-CWT, 3-CWT, 5-CWT, and 7-CWT corresponding to 1, 3, 5, and 7wt%, respectively. Systematic characterization using spectroscopic and microscopic techniques were employed to validate the successful preparation of the photocatalysts. Enhanced optoelectronic and photoelectrochemical properties were observed for the WO₃@Ti₃C2@g-C₃N4 heterostructure with respect to the individual materials. Photoluminescence spectra and Nyquist plots show restrained recombination rates and improved photocarrier conductivities, respectively, and this was credited to the synergistic coupling effect and the presence of highly conductive Ti₃C2 MXene. The strong interfacial contact surfaces upon the formation of the composite were confirmed using XPS. Multiple charge transfer mechanisms were proposed for the WO3@Ti3C₂@g-C3N4, which couples Z-scheme and Schottky-junction mediated with Ti3C2 MXene. Bode phase plots show improved charge carrier life-times upon the formation of the multijunctional photocatalyst. Moreover, transient photocurrent density of 7-CWT is 40 and seven (7) times higher compared to that of g-C₃N4 and WO3, correspondingly. Unlike in the traditional Z-Scheme, the formed ternary heterostructure possesses interfaces through the metallic 2D Ti₃C₂ MXene, which provided charge transfer channels for efficient photocarrier transfers with carrier concentrations (ND) of 17.49×1021 cm-3 and 4.86% photo-to-chemical conversion efficiency. The as-prepared ternary g-C₃N₄@WO₃@Ti₃C₂Tx exhibited excellent photoelectrochemical properties with reserved redox band potential potencies to facilitate efficient photo-oxidation and -reduction reactions. The fabricated multijunction photocatalyst exhibits potentials to be used in an extensive range of photocatalytic process vis., production of valuable hydrocarbons from CO₂, production of H₂, and degradation of a plethora of pollutants from wastewater.

Keywords: photocatalysis, Z-scheme, multijunction heterostructure, Ti₃C₂ MXene, g-C₃N₄

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223 Intriguing Modulations in the Excited State Intramolecular Proton Transfer Process of Chrysazine Governed by Host-Guest Interactions with Macrocyclic Molecules

Authors: Poojan Gharat, Haridas Pal, Sharmistha Dutta Choudhury

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Tuning photophysical properties of guest dyes through host-guest interactions involving macrocyclic hosts are the attractive research areas since past few decades, as these changes can directly be implemented in chemical sensing, molecular recognition, fluorescence imaging and dye laser applications. Excited state intramolecular proton transfer (ESIPT) is an intramolecular prototautomerization process display by some specific dyes. The process is quite amenable to tunability by the presence of different macrocyclic hosts. The present study explores the interesting effect of p-sulfonatocalix[n]arene (SCXn) and cyclodextrin (CD) hosts on the excited-state prototautomeric equilibrium of Chrysazine (CZ), a model antitumour drug. CZ exists exclusively in its normal form (N) in the ground state. However, in the excited state, the excited N* form undergoes ESIPT along with its pre-existing intramolecular hydrogen bonds, giving the excited state prototautomer (T*). Accordingly, CZ shows a single absorption band due to N form, but two emission bands due to N* and T* forms. Facile prototautomerization of CZ is considerably inhibited when the dye gets bound to SCXn hosts. However, in spite of lower binding affinity, the inhibition is more profound with SCX6 host as compared to SCX4 host. For CD-CZ system, while prototautomerization process is hindered by the presence of β-CD, it remains unaffected in the presence of γCD. Reduction in the prototautomerization process of CZ by SCXn and βCD hosts is unusual, because T* form is less dipolar in nature than the N*, hence binding of CZ within relatively hydrophobic hosts cavities should have enhanced the prototautomerization process. At the same time, considering the similar chemical nature of two CD hosts, their effect on prototautomerization process of CZ would have also been similar. The atypical effects on the prototautomerization process of CZ by the studied hosts are suggested to arise due to the partial inclusion or external binding of CZ with the hosts. As a result, there is a strong possibility of intermolecular H-bonding interaction between CZ dye and the functional groups present at the portals of SCXn and βCD hosts. Formation of these intermolecular H-bonds effectively causes the pre-existing intramolecular H-bonding network within CZ molecule to become weak, and this consequently reduces the prototautomerization process for the dye. Our results suggest that rather than the binding affinity between the dye and host, it is the orientation of CZ in the case of SCXn-CZ complexes and the binding stoichiometry in the case of CD-CZ complexes that play the predominant role in influencing the prototautomeric equilibrium of the dye CZ. In the case of SCXn-CZ complexes, the results obtained through experimental findings are well supported by quantum chemical calculations. Similarly for CD-CZ systems, binding stoichiometries obtained through geometry optimization studies on the complexes between CZ and CD hosts correlate nicely with the experimental results. Formation of βCD-CZ complexes with 1:1 stoichiometry while formation of γCD-CZ complexes with 1:1, 1:2 and 2:2 stoichiometries are revealed from geometry optimization studies and these results are in good accordance with the observed effects by the βCD and γCD hosts on the ESIPT process of CZ dye.

Keywords: intermolecular proton transfer, macrocyclic hosts, quantum chemical studies, photophysical studies

Procedia PDF Downloads 101