Search results for: solid fuel
Commenced in January 2007
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Edition: International
Paper Count: 3586

Search results for: solid fuel

106 Case Report of Left Atrial Myxoma Diagnosed by Bedside Echocardiography

Authors: Anthony S. Machi, Joseph Minardi

Abstract:

We present a case report of left atrial myxoma diagnosed by bedside transesophageal (TEE) ultrasound. Left atrial myxoma is the most common benign cardiac tumor and can obstruct blood flow and cause valvular insufficiency. Common symptoms consist of dyspnea, pulmonary edema and other features of left heart failure in addition to thrombus release in the form of tumor fragments. The availability of bedside ultrasound equipment is essential for the quick diagnosis and treatment of various emergency conditions including cardiac neoplasms. A 48-year-old Caucasian female with a four-year history of an untreated renal mass and anemia presented to the ED with two months of sharp, intermittent, bilateral flank pain radiating into the abdomen. She also reported intermittent vomiting and constipation along with generalized body aches, night sweats, and 100-pound weight loss over last year. She had a CT in 2013 showing a 3 cm left renal mass and a second CT in April 2016 showing a 3.8 cm left renal mass along with a past medical history of diverticulosis, chronic bronchitis, dyspnea on exertion, uncontrolled hypertension, and hyperlipidemia. Her maternal family history is positive for breast cancer, hypertension, and Type II Diabetes. Her paternal family history is positive for stroke. She was a current everyday smoker with an 11 pack/year history. Alcohol and drug use were denied. Physical exam was notable for a Grade II/IV systolic murmur at the right upper sternal border, dyspnea on exertion without angina, and a tender left lower quadrant. Her vitals and labs were notable for a blood pressure of 144/96, heart rate of 96 beats per minute, pulse oximetry of 96%, hemoglobin of 7.6 g/dL, hypokalemia, hypochloremia, and multiple other abnormalities. Physicians ordered a CT to evaluate her flank pain which revealed a 7.2 x 8.9 x 10.5 cm mixed cystic/solid mass in the lower pole of the left kidney and a filling defect in the left atrium. Bedside TEE was ordered to follow up on the filling defect. TEE reported an ejection fraction of 60-65% and visualized a mobile 6 x 3 cm mass in the left atrium attached to the interatrial septum extending into the mitral valve. Cardiothoracic Surgery and Urology were consulted and confirmed a diagnosis of left atrial myxoma and clear cell renal cell carcinoma. The patient returned a week later due to worsening nausea and vomiting and underwent emergent nephrectomy, lymph node dissection, and colostomy due to a necrotic colon. Her condition declined over the next four months due to lung and brain metastases, infections, and other complications until she passed away.

Keywords: bedside ultrasound, echocardiography, emergency medicine, left atrial myxoma

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105 Superoleophobic Nanocellulose Aerogel Membrance as Bioinspired Cargo Carrier on Oil by Sol-Gel Method

Authors: Zulkifli, I. W. Eltara, Anawati

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Understanding the complementary roles of surface energy and roughness on natural nonwetting surfaces has led to the development of a number of biomimetic superhydrophobic surfaces, which exhibit apparent contact angles with water greater than 150 degrees and low contact angle hysteresis. However, superoleophobic surfaces—those that display contact angles greater than 150 degrees with organic liquids having appreciably lower surface tensions than that of water—are extremely rare. In addition to chemical composition and roughened texture, a third parameter is essential to achieve superoleophobicity, namely, re-entrant surface curvature in the form of overhang structures. The overhangs can be realized as fibers. Superoleophobic surfaces are appealing for example, antifouling, since purely superhydrophobic surfaces are easily contaminated by oily substances in practical applications, which in turn will impair the liquid repellency. On the other studied have demonstrate that such aqueous nanofibrillar gels are unexpectedly robust to allow formation of highly porous aerogels by direct water removal by freeze-drying, they are flexible, unlike most aerogels that suffer from brittleness, and they allow flexible hierarchically porous templates for functionalities, e.g. for electrical conductivity. No crosslinking, solvent exchange nor supercritical drying are required to suppress the collapse during the aerogel preparation, unlike in typical aerogel preparations. The aerogel used in current work is an ultralight weight solid material composed of native cellulose nanofibers. The native cellulose nanofibers are cleaved from the self-assembled hierarchy of macroscopic cellulose fibers. They have become highly topical, as they are proposed to show extraordinary mechanical properties due to their parallel and grossly hydrogen bonded polysaccharide chains. We demonstrate that superoleophobic nanocellulose aerogels coating by sol-gel method, the aerogel is capable of supporting a weight nearly 3 orders of magnitude larger than the weight of the aerogel itself. The load support is achieved by surface tension acting at different length scales: at the macroscopic scale along the perimeter of the carrier, and at the microscopic scale along the cellulose nanofibers by preventing soaking of the aerogel thus ensuring buoyancy. Superoleophobic nanocellulose aerogels have recently been achieved using unmodified cellulose nanofibers and using carboxy methylated, negatively charged cellulose nanofibers as starting materials. In this work, the aerogels made from unmodified cellulose nanofibers were subsequently treated with fluorosilanes. To complement previous work on superoleophobic aerogels, we demonstrate their application as cargo carriers on oil, gas permeability, plastrons, and drag reduction, and we show that fluorinated nanocellulose aerogels are high-adhesive superoleophobic surfaces. We foresee applications including buoyant, gas permeable, dirt-repellent coatings for miniature sensors and other devices floating on generic liquid surfaces.

Keywords: superoleophobic, nanocellulose, aerogel, sol-gel

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104 Developing a Sustainable Transit Planning Index Using Analytical Hierarchy Process Method for ZEB Implementation in Canada

Authors: Mona Ghafouri-Azar, Sara Diamond, Jeremy Bowes, Grace Yuan, Aimee Burnett, Michelle Wyndham-West, Sara Wagner, Anand Pariyarath

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Transportation is the fastest growing source of greenhouse gas emissions worldwide. In Canada, it is responsible for 23% of total CO2emissions from fuel combustion, and emissions from the transportation sector are the second largest source of emissions after the oil and gas sector. Currently, most Canadian public transportation systems rely on buses that operateon fossil fuels.Canada is currently investing billions of dollars to replacediesel buses with electric busesas this isperceived to have a significant impact on climate mitigation. This paper focuses on the possible impacts of zero emission buses (ZEB) on sustainable development, considering three dimensions of sustainability; environmental quality, economic growth, and social development.A sustainable transportation system is one that is safe, affordable, accessible, efficient, and resilient and that contributes minimal emissions of carbon and other pollutants.To enable implementation of these goals, relevant indicators were selected and defined that measure progress towards a sustainable transportation system. These were drawn from Canadian and international examples. Studies compare different European cities in terms of development, sustainability, and infrastructures, by using transport performance indicators. A Normalized Transport Sustainability index measures and compares policies in different urban areas and allows fine-tuning of policies. Analysts use a number ofmethods for sustainable analysis, like cost-benefit analysis (CBA) toassess economic benefit, life-cycle assessment (LCA) to assess social, economic, and environment factors and goals, and multi-criteria decision making (MCDM) analysis which can comparediffering stakeholder preferences.A multi criteria decision making approach is an appropriate methodology to plan and evaluate sustainable transit development and to provide insights and meaningful information for decision makers and transit agencies. It is essential to develop a system thataggregates specific discrete indices to assess the sustainability of transportation systems.Theseprioritize indicators appropriate for the differentCanadian transit system agencies and theirpreferences and requirements. This studywill develop an integrating index that alliesexistingdiscrete indexes to supporta reliable comparison between the current transportation system (diesel buses) and the new ZEB system emerging in Canada. As a first step, theindexes for each category are selected, and the index matrix constructed. Second, the selected indicators arenormalized to remove anyinconsistency between them. Next, the normalized matrix isweighted based on the relative importance of each index to the main domains of sustainability using the analytical hierarchy process (AHP) method. This is accomplished through expert judgement around the relative importance of different attributes with respect to the goals through apairwise comparison matrix. The considerationof multiple environmental, economic, and social factors (including equity and health) is integrated intoa sustainable transit planning index (STPI) which supportsrealistic ZEB implementation in Canada and beyond and is useful to different stakeholders, agencies, and ministries.

Keywords: zero emission buses, sustainability, sustainable transit, transportation, analytical hierarchy process, environment, economy, social

Procedia PDF Downloads 101
103 Living in the Edge: Crisis in Indian Tea Industry and Social Deprivation of Tea Garden Workers in Dooars Region of India

Authors: Saraswati Kerketta

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Tea industry is one of the oldest organised sector of India. It employs roughly 1.5 million people directly. Since the last decade Indian tea industry, especially in the northern region is experiencing worst crisis in the post-independence period. Due to many reason the prices of tea show steady decline. The workers are paid one of the lowest wage in tea industry in the world (1.5$ a day) below the UN's $2 a day for extreme poverty. The workers rely on addition benefits from plantation which includes food, housing and medical facilities. These have been effective means of enslavement of generations of labourers by the owners. There is hardly any change in the tea estates where the owners determine the fate of workers. When the tea garden is abandoned or is closed all the facilities disappear immediately. The workers are the descendants of tribes from central India also known as 'tea tribes'. Alienated from their native place, the geographical and social isolation compounded their vulnerability of these people. The economy of the region being totally dependent on tea has resulted in absolute unemployment for the workers of these tea gardens. With no other livelihood and no land to grow food, thousands of workers faced hunger and starvation. The Plantation Labour Act which ensures the decent working and living condition is violated continuously. The labours are forced to migrate and are also exposed to the risk of human trafficking. Those who are left behind suffers from starvation, malnutrition and disease. The condition in the sick tea plantation is no better. Wage are not paid regularly, subsidised food, fuel are also not supplied properly. Health care facilities are in very bad shape. Objectives: • To study the socio-cultural and demographic characteristics of the tea garden labourers in the study area. • To examine the social situation of workers in sick estates in dooars region. • To assess the magnitude of deprivation the impact of economic crisis on abandoned and closed tea estates in the region. Data Base: The study is based on data collected from field survey. Methods: Quantative: Cross-Tabulation, Regression analysis. Qualitative: Household Survey, Focussed Group Discussion, In-depth interview of key informants. Findings: Purchasing power parity has declined since in last three decades. There has been many fold increase in migration. Males migrates long distance towards central and west and south India. Females and children migrates both long and short distance. No one has reported to migrate back to the place of origin of their ancestors. Migrant males work mostly as construction labourers and as factory workers whereas females and children work as domestic help and construction labourers. In about 37 cases either they haven't contacted their families in last six months or are not traceable. The families with single earning members are more likely to migrate. Burden of disease and the duration of sickness, abandonment and closure of plantation are closely related. Death tolls are likely to rise 1.5 times in sick tea gardens and three times in closed tea estates. Sixty percent of the people are malnourished in the sick tea gardens and more than eighty five per cent in abandoned and sick tea gardens.

Keywords: migration, trafficking, starvation death, tea garden workers

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102 Fermented Fruit and Vegetable Discard as a Source of Feeding Ingredients and Functional Additives

Authors: Jone Ibarruri, Mikel Manso, Marta Cebrián

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A high amount of food is lost or discarded in the World every year. In addition, in the last decades, an increasing demand of new alternative and sustainable sources of proteins and other valuable compounds is being observed in the food and feeding sectors and, therefore, the use of food by-products as nutrients for these purposes sounds very interesting from the environmental and economical point of view. However, the direct use of discarded fruit and vegetables that present, in general, a low protein content is not interesting as feeding ingredient except if they are used as a source of fiber for ruminants. Especially in the case of aquaculture, several alternatives to the use of fish meal and other vegetable protein sources have been extensively explored due to the scarcity of fish stocks and the unsustainability of fishing for these purposes. Fish mortality is also of great concern in this sector as this problem highly reduces their economic feasibility. So, the development of new functional and natural ingredients that could reduce the need for vaccination is also of great interest. In this work, several fermentation tests were developed at lab scale using a selected mixture of fruit and vegetable discards from a wholesale market located in the Basque Country to increase their protein content and also to produce some bioactive extracts that could be used as additives in aquaculture. Fruit and vegetable mixtures (60/40 ww) were centrifugated for humidity reduction and crushed to 2-5 mm particle size. Samples were inoculated with a selected Rhizopus oryzae strain and fermented for 7 days in controlled conditions (humidity between 65 and 75% and 28ºC) in Petri plates (120 mm) by triplicate. Obtained results indicated that the final fermented product presented a twofold protein content (from 13 to 28% d.w). Fermented product was further processed to determine their possible functionality as a feed additive. Extraction tests were carried out to obtain an ethanolic extract (60:40 ethanol: water, v.v) and remaining biomass that also could present applications in food or feed sectors. The extract presented a polyphenol content of about 27 mg GAE/gr d.w with antioxidant activity of 8.4 mg TEAC/g d.w. Remining biomass is mainly composed of fiber (51%), protein (24%) and fat (10%). Extracts also presented antibacterial activity according to the results obtained in Agar Diffusion and to the Minimum Inhibitory Concentration (MIC) tests determined against several food and fish pathogen strains. In vitro, digestibility was also assessed to obtain preliminary information about the expected effect of extraction procedure on fermented product digestibility. First results indicated that remaining biomass after extraction doesn´t seem to improve digestibility in comparison to the initial fermented product. These preliminary results show that fermented fruit and vegetables can be a useful source of functional ingredients for aquaculture applications and a substitute of other protein sources in the feeding sector. Further validation will be also carried out through “in vivo” tests with trout and bass.

Keywords: fungal solid state fermentation, protein increase, functional extracts, feed ingredients

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101 Working Without a Safety Net: Exploring Struggles and Dilemmas Faced by Greek Orthodox Married Clergy Through a Mental Health Lens, in the Australian Context

Authors: Catherine Constantinidis (Nee Tsacalos)

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This paper presents one aspect of the larger Masters qualitative study exploring the roles of married Greek Orthodox clergy, the Priest and Presbytera, under the wing of the Greek Orthodox Archdiocese of Australia. This ground breaking research necessitated the creation of primary data within a phenomenological paradigm drawing from lived experiences of the Priests and Presbyteres in contemporary society. As a Social Worker, a bilingual (Greek/English) Mental Health practitioner and a Presbytera, the questions constantly raised and pondered are: Who do the Priest and Presbytera turn to when they experience difficulties or problems? Where do they go for support? What is in place for their emotional and psychological health and well-being? Who cares for the spiritual carer? Who is there to catch our falling clergy and their wives? What is their 'safety net'? Identified phenomena of angst, stress, frustration and confusion experienced by the Priest and (by extension) the Presbytera, within their position, coupled with basic assumptions, perceptions and expectations about their roles, the role of the organisation (the Church), and their role as spouse often caused confusion and in some cases conflict. Unpacking this complex and multi-dimensional relationship highlighted not only the roller coaster of emotions, potentially affecting their physical and mental health, but also the impact on the interwoven relationships of marriage and ministry. The author considers these phenomena in the light of bilingual cultural and religious organisational practice frameworks, specifically the Greek Orthodox Church, whilst filtering these findings through a mental health lens. One could argue that it is an expectation that clergy (and by default their wives) take on the responsibility to be kind, nurturing and supportive to others. However, when it comes to taking care of self, they are not nearly as kind. This research looks at a recurrent theme throughout the interviews where all participants talked about limited support systems and poor self care strategies and the impact this has on their ministry, mental, emotional, and physical health and ultimately on their relationships with self and others. The struggle all participants encountered at some point in their ministry was physical, spiritual and psychological burn out. The overall aim of the researcher is to provide a voice for the Priest and the Presbytera painting a clearer picture of these roles and facilitating an awareness of struggles and dilemmas faced in their ministry. It is hoped these identified gaps in self care strategies and support systems will provide solid foundations for building a culturally sensitive, empathetic and effective support system framework, incorporating the spiritual and psychological well-being of the Priest and Presbytera, a ‘safety net’. A supplementary aim is to inform and guide ministry practice frameworks for clergy, spouses, the church hierarchy and religious organisations on a local and global platform incorporating some sort of self-care system.

Keywords: care for the carer, mental health, Priest, Presbytera, religion, support system

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100 Recent Findings of Late Bronze Age Mining and Archaeometallurgy Activities in the Mountain Region of Colchis (Southern Lechkhumi, Georgia)

Authors: Rusudan Chagelishvili, Nino Sulava, Tamar Beridze, Nana Rezesidze, Nikoloz Tatuashvili

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The South Caucasus is one of the most important centers of prehistoric metallurgy, known for its Colchian bronze culture. Modern Lechkhumi – historical Mountainous Colchis where the existence of prehistoric metallurgy is confirmed by the discovery of many artifacts is a part of this area. Studies focused on prehistoric smelting sites, related artefacts, and ore deposits have been conducted during last ten years in Lechkhumi. More than 20 prehistoric smelting sites and artefacts associated with metallurgical activities (ore roasting furnaces, slags, crucible, and tuyères fragments) have been identified so far. Within the framework of integrated studies was established that these sites were operating in 13-9 centuries B.C. and used for copper smelting. Palynological studies of slags revealed that chestnut (Castanea sativa) and hornbeam (Carpinus sp.) wood were used as smelting fuel. Geological exploration-analytical studies revealed that copper ore mining, processing, and smelting sites were distributed close to each other. Despite recent complex data, the signs of prehistoric mines (trenches) haven’t been found in this part of the study area so far. Since 2018 the archaeological-geological exploration has been focused on the southern part of Lechkhumi and covered the areas of villages Okureshi and Opitara. Several copper smelting sites (Okureshi 1 and 2, Opitara 1), as well as a Colchian Bronze culture settlement, have been identified here. Three mine workings have been found in the narrow gorge of the river Rtkhmelebisgele in the vicinities of the village Opitara. In order to establish a link between the Opitara-Okureshi archaeometallurgical sites, Late Bronze Age settlements, and mines, various scientific analytical methods -mineralized rock and slags petrography and atomic absorption spectrophotometry (AAS) analysis have been applied. The careful examination of Opitara mine workings revealed that there is a striking difference between the mine #1 on the right bank of the river and mines #2 and #3 on the left bank. The first one has all characteristic features of the Soviet period mine working (e. g. high portal with angular ribs and roof showing signs of blasting). In contrast, mines #2 and #3, which are located very close to each other, have round-shaped portals/entrances, low roofs, and fairly smooth ribs and are filled with thick layers of river sediments and collapsed weathered rock mass. A thorough review of the publications related to prehistoric mine workings revealed some striking similarities between mines #2 and #3 with their worldwide analogues. Apparently, the ore extraction from these mines was conducted by fire-setting applying primitive tools. It was also established that mines are cut in Jurassic mineralized volcanic rocks. Ore minerals (chalcopyrite, pyrite, galena) are related to calcite and quartz veins. The results obtained through the petrochemical and petrography studies of mineralized rock samples from Opitara mines and prehistoric slags are in complete correlation with each other, establishing the direct link between copper mining and smelting within the study area. Acknowledgment: This work was supported by the Shota Rustaveli National Science Foundation of Georgia (grant # FR-19-13022).

Keywords: archaeometallurgy, Mountainous Colchis, mining, ore minerals

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99 Study of Nucleation and Growth Processes of Ettringite in Supersaturated Diluted Solutions

Authors: E. Poupelloz, S. Gauffinet

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Ettringite Ca₆Al₂(SO₄)₃(OH)₁₂26H₂O is one of the major hydrates formed during cement hydration. Ettringite forms in Portland cement from the reaction between tricalcium aluminate Ca₃Al₂O₆ and calcium sulfate. Ettringite is also present in calcium sulfoaluminate cement in which it is the major hydrate, formed by the reaction between yeelimite Ca₄(AlO₂)₆SO₄ and calcium sulfate. About the formation of ettringite, numerous results are available in the literature even if some issues are still under discussion. However, almost all published work about ettringite was done on cementitious systems. Yet in cement, hydration reactions are very complex, the result of dissolution-precipitation processes and are submitted to various interactions. Understanding the formation process of a phase alone, here ettringite, is the first step to later understand the much more complex reactions happening in cement. This study is crucial for the comprehension of early cement hydration and physical behavior. Indeed formation of hydrates, in particular, ettringite, will have an influence on the rheological properties of the cement paste and on the need for admixtures. To make progress toward the understanding of existing phenomena, a specific study of nucleation and growth processes of ettringite was conducted. First ettringite nucleation was studied in ionic aqueous solutions, with controlled but different experimental conditions, as different supersaturation degrees (β), different pH or presence of exogenous ions. Through induction time measurements, interfacial ettringite crystals solution energies (γ) were determined. Growth of ettringite in supersaturated solutions was also studied through chain crystallization reactions. Specific BET surface area measurements and Scanning Electron Microscopy observations seemed to prove that growth process is favored over the nucleation process when ettringite crystals are initially present in a solution with a low supersaturation degree. The influence of stirring on ettringite formation was also investigated. Observation was made that intensity and nature of stirring have a high influence on the size of ettringite needles formed. Needle sizes vary from less than 10µm long depending on the stirring to almost 100µm long without any stirring. During all previously mentioned experiments, initially present ions are consumed to form ettringite in such a way that the supersaturation degree with regard to ettringite is decreasing over time. To avoid this phenomenon a device compensating the drop of ion concentrations by adding some more solutions, and therefore always have constant ionic concentrations, was used. This constant β recreates the conditions of the beginning of cement paste hydration, when the dissolution of solid reagents compensates the consumption of ions to form hydrates. This device allowed the determination of the ettringite precipitation rate as a function of the supersaturation degree β. Taking samples at different time during ettringite precipitation and doing BET measurements allowed the determination of the interfacial growth rate of ettringite in m²/s. This work will lead to a better understanding and control of ettringite formation alone and thus during cements hydration. This study will also ultimately define the impact of ettringite formation process on the rheology of cement pastes at early age, which is a crucial parameter from a practical point of view.

Keywords: cement hydration, ettringite, morphology of crystals, nucleation-growth process

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98 Energy Efficiency of Secondary Refrigeration with Phase Change Materials and Impact on Greenhouse Gases Emissions

Authors: Michel Pons, Anthony Delahaye, Laurence Fournaison

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Secondary refrigeration consists of splitting large-size direct-cooling units into volume-limited primary cooling units complemented by secondary loops for transporting and distributing cold. Such a design reduces the refrigerant leaks, which represents a source of greenhouse gases emitted into the atmosphere. However, inserting the secondary circuit between the primary unit and the ‘users’ heat exchangers (UHX) increases the energy consumption of the whole process, which induces an indirect emission of greenhouse gases. It is thus important to check whether that efficiency loss is sufficiently limited for the change to be globally beneficial to the environment. Among the likely secondary fluids, phase change slurries offer several advantages: they transport latent heat, they stabilize the heat exchange temperature, and the formerly evaporators still can be used as UHX. The temperature level can also be adapted to the desired cooling application. Herein, the slurry {ice in mono-propylene-glycol solution} (melting temperature Tₘ of 6°C) is considered for food preservation, and the slurry {mixed hydrate of CO₂ + tetra-n-butyl-phosphonium-bromide in aqueous solution of this salt + CO₂} (melting temperature Tₘ of 13°C) is considered for air conditioning. For the sake of thermodynamic consistency, the analysis encompasses the whole process, primary cooling unit plus secondary slurry loop, and the various properties of the slurries, including their non-Newtonian viscosity. The design of the whole process is optimized according to the properties of the chosen slurry and under explicit constraints. As a first constraint, all the units must deliver the same cooling power to the user. The other constraints concern the heat exchanges areas, which are prescribed, and the flow conditions, which prevent deposition of the solid particles transported in the slurry, and their agglomeration. Minimization of the total energy consumption leads to the optimal design. In addition, the results are analyzed in terms of exergy losses, which allows highlighting the couplings between the primary unit and the secondary loop. One important difference between the ice-slurry and the mixed-hydrate one is the presence of gaseous carbon dioxide in the latter case. When the mixed-hydrate crystals melt in the UHX, CO₂ vapor is generated at a rate that depends on the phase change kinetics. The flow in the UHX, and its heat and mass transfer properties are significantly modified. This effect has never been investigated before. Lastly, inserting the secondary loop between the primary unit and the users increases the temperature difference between the refrigerated space and the evaporator. This results in a loss of global energy efficiency, and therefore in an increased energy consumption. The analysis shows that this loss of efficiency is not critical in the first case (Tₘ = 6°C), while the second case leads to more ambiguous results, partially because of the higher melting temperature.The consequences in terms of greenhouse gases emissions are also analyzed.

Keywords: exergy, hydrates, optimization, phase change material, thermodynamics

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97 Electrochemical Properties of Li-Ion Batteries Anode Material: Li₃.₈Cu₀.₁Ni₀.₁Ti₅O₁₂

Authors: D. Olszewska, J. Niewiedzial

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In some types of Li-ion batteries carbon in the form of graphite is used. Unfortunately, carbon materials, in particular graphite, have very good electrochemical properties, but increase their volume during charge/discharge cycles, which may even lead to an explosion of the cell. The cell element may be replaced by a composite material consisting of lithium-titanium oxide Li4Ti5O12 (LTO) modified with copper and nickel ions and carbon derived from sucrose. This way you can improve the conductivity of the material. LTO is appropriate only for applications which do not require high energy density because of its high operating voltage (ca. 1.5 V vs. Li/Li+). Specific capacity of Li4Ti5O12 is high enough for utilization in Li-ion batteries (theoretical capacity 175 mAh·g-1) but it is lower than capacity of graphite anodes. Materials based on Li4Ti5O12 do not change their volume during charging/discharging cycles, however, LTO has low conductivity. Another positive aspect of the use of sucrose in the carbon composite material is to eliminate the addition of carbon black from the anode of the battery. Therefore, the proposed materials contribute significantly to environmental protection and safety of selected lithium cells. New anode materials in order to obtain Li3.8Cu0.1Ni0.1Ti5O12 have been prepared by solid state synthesis using three-way: i) stoichiometric composition of Li2CO3, TiO2, CuO, NiO (A- Li3.8Cu0.1Ni0.1Ti5O12); ii) stoichiometric composition of Li2CO3, TiO2, Cu(NO3)2, Ni(NO3)2 (B-Li3.8Cu0.1Ni0.1Ti5O12); and iii) stoichiometric composition of Li2CO3, TiO2, CuO, NiO calcined with 10% of saccharose (Li3.8Cu0.1Ni0.1Ti5O12-C). Structure of materials was studied by X-ray diffraction (XRD). The electrochemical properties were performed using appropriately prepared cell Li|Li+|Li3.8Cu0.1Ni0.1Ti5O12 for cyclic voltammetry and discharge/charge measurements. The cells were periodically charged and discharged in the voltage range from 1.3 to 2.0 V applying constant charge/discharge current in order to determine the specific capacity of each electrode. Measurements at various values of the charge/discharge current (from C/10 to 5C) were carried out. Cyclic voltammetry investigation was carried out by applying to the cells a voltage linearly changing over time at a rate of 0.1 mV·s-1 (in the range from 2.0 to 1.3 V and from 1.3 to 2.0 V). The XRD method analyzes show that composite powders were obtained containing, in addition to the main phase, 4.78% and 4% TiO2 in A-Li3.8Cu0.1Ni0.1O12 and B-Li3.8Cu0.1Ni0.1O12, respectively. However, Li3.8Cu0.1Ni0.1O12-C material is three-phase: 63.84% of the main phase, 17.49 TiO2 and 18.67 Li2TiO3. Voltammograms of electrodes containing materials A-Li3.8Cu0.1Ni0.1O12 and B-Li3.8Cu0.1Ni0.1O12 are correct and repeatable. Peak cathode occurs for both samples at a potential approx. 1.52±0.01 V relative to a lithium electrode, while the anodic peak at potential approx. 1.65±0.05 V relative to a lithium electrode. Voltammogram of Li3.8Cu0.1Ni0.1Ti5O12-C (especially for the first measurement cycle) is not correct. There are large variations in values of specific current, which are not characteristic for materials LTO. From the point of view of safety and environmentally friendly production of Li-ion cells eliminating soot and applying Li3.8Cu0.1Ni0.1Ti5O12-C as an active material of an anode in lithium-ion batteries seems to be a good alternative to currently used materials.

Keywords: anode, Li-ion batteries, Li₄O₅O₁₂, spinel

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96 Analytical and Numerical Modeling of Strongly Rotating Rarefied Gas Flows

Authors: S. Pradhan, V. Kumaran

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Centrifugal gas separation processes effect separation by utilizing the difference in the mole fraction in a high speed rotating cylinder caused by the difference in molecular mass, and consequently the centrifugal force density. These have been widely used in isotope separation because chemical separation methods cannot be used to separate isotopes of the same chemical species. More recently, centrifugal separation has also been explored for the separation of gases such as carbon dioxide and methane. The efficiency of separation is critically dependent on the secondary flow generated due to temperature gradients at the cylinder wall or due to inserts, and it is important to formulate accurate models for this secondary flow. The widely used Onsager model for secondary flow is restricted to very long cylinders where the length is large compared to the diameter, the limit of high stratification parameter, where the gas is restricted to a thin layer near the wall of the cylinder, and it assumes that there is no mass difference in the two species while calculating the secondary flow. There are two objectives of the present analysis of the rarefied gas flow in a rotating cylinder. The first is to remove the restriction of high stratification parameter, and to generalize the solutions to low rotation speeds where the stratification parameter may be O (1), and to apply for dissimilar gases considering the difference in molecular mass of the two species. Secondly, we would like to compare the predictions with molecular simulations based on the direct simulation Monte Carlo (DSMC) method for rarefied gas flows, in order to quantify the errors resulting from the approximations at different aspect ratios, Reynolds number and stratification parameter. In this study, we have obtained analytical and numerical solutions for the secondary flows generated at the cylinder curved surface and at the end-caps due to linear wall temperature gradient and external gas inflow/outflow at the axis of the cylinder. The effect of sources of mass, momentum and energy within the flow domain are also analyzed. The results of the analytical solutions are compared with the results of DSMC simulations for three types of forcing, a wall temperature gradient, inflow/outflow of gas along the axis, and mass/momentum input due to inserts within the flow. The comparison reveals that the boundary conditions in the simulations and analysis have to be matched with care. The commonly used diffuse reflection boundary conditions at solid walls in DSMC simulations result in a non-zero slip velocity as well as a temperature slip (gas temperature at the wall is different from wall temperature). These have to be incorporated in the analysis in order to make quantitative predictions. In the case of mass/momentum/energy sources within the flow, it is necessary to ensure that the homogeneous boundary conditions are accurately satisfied in the simulations. When these precautions are taken, there is excellent agreement between analysis and simulations, to within 10 %, even when the stratification parameter is as low as 0.707, the Reynolds number is as low as 100 and the aspect ratio (length/diameter) of the cylinder is as low as 2, and the secondary flow velocity is as high as 0.2 times the maximum base flow velocity.

Keywords: rotating flows, generalized onsager and carrier-Maslen model, DSMC simulations, rarefied gas flow

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95 Population Diversity of Dalmatian Pyrethrum Based on Pyrethrin Content and Composition

Authors: Filip Varga, Nina Jeran, Martina Biosic, Zlatko Satovic, Martina Grdisa

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Dalmatian pyrethrum (Tanacetum cinerariifolium /Trevir./ Sch. Bip.), a species endemic to the eastern Adriatic coastline, is the source of natural insecticide pyrethrin. Pyrethrin is a mixture of six compounds (pyrethrin I and II, cinerin I and II, jasmolin I and II) that exhibits high insecticidal activity with no detrimental effects to the environment. A recently optimized matrix-solid phase dispersion method (MSPD), using florisil as the sorbent, acetone-ethyl acetate (1:1, v/v) as the elution solvent, and sodium sulfate anhydrous as the drying agent was utilized to extract the pyrethrins from 10 wild populations (20 individuals per population) distributed along the Croatian coast. All six components in the extracts were qualitatively and quantitatively determined by high-performance liquid chromatography with a diode array detector (HPLC-DAD). Pearson’s correlation index was calculated between pyrethrin compounds, and differences between the populations using the analysis of variance were tested. Additionally, the correlation of each pyrethrin component with spatio-ecological variables (bioclimate, soil properties, elevation, solar radiation, and distance from the coastline) was calculated. Total pyrethrin content ranged from 0.10% to 1.35% of dry flower weight, averaging 0.58% across all individuals. Analysis of variance revealed significant differences between populations based on all six pyrethrin compounds and total pyrethrin content. On average, the lowest total pyrethrin content was found in the population from Pelješac peninsula (0.22% of dry flower weight) in which total pyrethrin content lower than 0.18% was detected in 55% of the individuals. The highest average total pyrethrin content was observed in the population from island Zlarin (0.87% of dry flower weight), in which total pyrethrin content higher than 1.00% was recorded in only 30% of the individuals. Pyrethrin I/pyrethrin II ratio as a measure of extract quality ranged from 0.21 (population from the island Čiovo) to 5.88 (population from island Mali Lošinj) with an average of 1.77 across all individuals. By far, the lowest quality of extracts was found in the population from Mt. Biokovo (pyrethrin I/II ratio lower than 0.72 in 40% of individuals) due to the high pyrethrin II content typical for this population. Pearson’s correlation index revealed a highly significant positive correlation between pyrethrin I content and total pyrethrin content and a strong negative correlation between pyrethrin I and pyrethrin II. The results of this research clearly indicate high intra- and interpopulation diversity of Dalmatian pyrethrum with regards to pyrethrin content and composition. The information obtained has potential use in plant genetic resources conservation and biodiversity monitoring. Possibly the largest potential lies in designing breeding programs aimed at increasing pyrethrin content in commercial breeding lines and reintroduction in agriculture in Croatia. Acknowledgment: This work has been fully supported by the Croatian Science Foundation under the project ‘Genetic background of Dalmatian pyrethrum (Tanacetum cinerariifolium /Trevir/ Sch. Bip.) insecticidal potential’ - (PyrDiv) (IP-06-2016-9034).

Keywords: Dalmatian pyrethrum, HPLC, MSPD, pyrethrin

Procedia PDF Downloads 115
94 The Walkway Project: An Exploration of Informal Public Space Upgrading in Gugulethu, Cape Town

Authors: Kathryn Ewing

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Safe and accessible public spaces are vital elements of our South African cities. Public spaces hold the potential to act as important, vibrant places for learning, exchange, and practice. Public walkways, however, are some of the most neglected and extremely dangerous public spaces experienced in the local neighborhood of Gugulethu in Cape Town. Walkways feel insignificant, being recognized as informal and undetermined or retain complex fragments of formal erven. They are generally out of sight connecting minor streets and informal settlements. Community residents refer to the walkways as unsafe and dirty spaces. Local authorities allocate minimal to no municipal budgets nor maintenance plans resulting in a lack of basic services, particularly lighting and green infrastructure. ‘The Walkway Project’ presents a series of urban stories collected from co-design workshops, emotional mapping exercises, and fieldwork, including urban walks and urban talks. The narrative interprets the socio-spatial practice and complexity of informal public space in Gugulethu, Cape Town. The Walkway Project research, interrelated to the Master of Urban Design teaching and design-research studio, has a strong focus on participatory and engaged learning and action research methodology within a deliberate pedagogy. A consolidated urban design implementation plan exposes the impact and challenges of waste and water, opening the debate on relevant local solutions for resilience and safety in Cape Town. A small and neglected passage connecting two streets, commonly referred to as iThemba Walkway, is presented as a case study to show-case strategic urban design intervention strategies for urban upgrading. The iThemba walkway is a community-driven project that demonstrates active and responsible co-design and participatory development opportunities. In March 2021, when visited on an urban walk, the public space was covered by rubble and solid waste. By April 2021, the community cleaned the walkway and created an accessible passage for the school children to pass. Numerous co-design workshops have taken place over the past year. The walkway has emerged as a public space upgrading project facilitated, motivated, and implemented by multiple local partners and residents. Social maps from urban walks and talks illustrate the transformation of iThemba Walkway into an inclusive, safe, resilient, and sustainable urban space, linked to Sustainable Development Goal number 11, sustainable cities and communities. The outcomes of the upgrading project facilitate a deeper understanding of co-design methods, urban upgrading processes, and monitoring of public space and informal urbanism.

Keywords: informal, public space, resilience, safety, upgrade, walkways

Procedia PDF Downloads 68
93 The Academic Experience of Vocational Training Teachers

Authors: Andréanne Gagné, Jo Anni Joncas, Éric Tendon

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Teaching in vocational training requires an excellent mastery of the trade being taught, but also solid professional skills in pedagogy. Teachers are typically recruited on the basis of their trade expertise, and they do not necessarily have training or experience in pedagogy. In order to counter this lack, the Ministry of Education (Québec, Canada) requires them to complete a 120-credit university program to obtain their teaching certificate. They must complete this training in addition to their teaching duties. This training was rarely planned in the teacher’s life course, and each teacher approaches it differently: some are enthusiastic, but many feel reluctant discouragement and even frustration at the idea of committing to a training program lasting an average of 10 years to completion. However, Quebec is experiencing an unprecedented shortage of teachers, and the perseverance of vocational teachers in their careers requires special attention because of the conditions of their specific integration conditions. Our research examines the perceptions that vocational teachers in training have of their academic experience in pre-service teaching. It differs from previous research in that it focuses on the influence of the academic experience on the teaching employment experience. The goal is that by better understanding the university experience of teachers in vocational education, we can identify support strategies to support their school experience and their teaching. To do this, the research is based on the theoretical framework of the sociology of experience, which allows us to study the way in which these “teachers-students” give meaning to their university program in articulation with their jobs according to three logics of action. The logic of integration is based on the process of socialization, where the action is preceded by the internalization of values, norms, and cultural models associated with the training context. The logic of strategy refers to the usefulness of this experience where the individual constructs a form of rationality according to his objectives, resources, social position, and situational constraints. The logic of subjectivation refers to reflexivity activities aimed at solving problems and making choices. These logics served as a framework for the development of an online questionnaire. Three hundred respondents, newly enrolled in an undergraduate teaching program (bachelor's degree in vocational education), expressed themselves about their academic experience. This paper relates qualitative data (open-ended questions) subjected to an interpretive repertory analysis approach to descriptive data (closed-ended questions) that emerged. The results shed light on how the respondents perceive themselves as teachers and students, their perceptions of university training and the support offered, and the place that training occupies in their professional path. Indeed, their professional and academic paths are inextricably linked, and it seems essential to take them into account simultaneously to better meet their needs and foster the development of their expertise in pedagogy. The discussion focuses on the strengths and limitations of university training from the perspective of the logic of action. The results also suggest support strategies that can be implemented to better support the integration and retention of student teachers in professional education.

Keywords: teacher, vocational training, pre-service training, academic experience

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92 Influence Study of the Molar Ratio between Solvent and Initiator on the Reaction Rate of Polyether Polyols Synthesis

Authors: María José Carrero, Ana M. Borreguero, Juan F. Rodríguez, María M. Velencoso, Ángel Serrano, María Jesús Ramos

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Flame-retardants are incorporated in different materials in order to reduce the risk of fire, either by providing increased resistance to ignition, or by acting to slow down combustion and thereby delay the spread of flames. In this work, polyether polyols with fire retardant properties were synthesized due to their wide application in the polyurethanes formulation. The combustion of polyurethanes is primarily dependent on the thermal properties of the polymer, the presence of impurities and formulation residue in the polymer as well as the supply of oxygen. There are many types of flame retardants, most of them are phosphorous compounds of different nature and functionality. The addition of these compounds is the most common method for the incorporation of flame retardant properties. The employment of glycerol phosphate sodium salt as initiator for the polyol synthesis allows obtaining polyols with phosphate groups in their structure. However, some of the critical points of the use of glycerol phosphate salt are: the lower reactivity of the salt and the necessity of a solvent (dimethyl sulfoxide, DMSO). Thus, the main aim in the present work was to determine the amount of the solvent needed to get a good solubility of the initiator salt. Although the anionic polymerization mechanism of polyether formation is well known, it seems convenient to clarify the role that DMSO plays at the starting point of the polymerization process. Regarding the fact that the catalyst deprotonizes the hydroxyl groups of the initiator and as a result of this, two water molecules and glycerol phosphate alkoxide are formed. This alkoxide, together with DMSO, has to form a homogeneous mixture where the initiator (solid) and the propylene oxide (PO) are soluble enough to mutually interact. The addition rate of PO increased when the solvent/initiator ratios studied were increased, observing that it also made the initiation step shorter. Furthermore, the molecular weight of the polyol decreased when higher solvent/initiator ratios were used, what revealed that more amount of salt was activated, initiating more chains of lower length but allowing to react more phosphate molecules and to increase the percentage of phosphorous in the final polyol. However, the final phosphorous content was lower than the theoretical one because only a percentage of salt was activated. On the other hand, glycerol phosphate disodium salt was still partially insoluble in DMSO studied proportions, thus, the recovery and reuse of this part of the salt for the synthesis of new flame retardant polyols was evaluated. In the recovered salt case, the rate of addition of PO remained the same than in the commercial salt but a shorter induction period was observed, this is because the recovered salt presents a higher amount of deprotonated hydroxyl groups. Besides, according to molecular weight, polydispersity index, FT-IR spectrum and thermal stability, there were no differences between both synthesized polyols. Thus, it is possible to use the recovered glycerol phosphate disodium salt in the same way that the commercial one.

Keywords: DMSO, fire retardants, glycerol phosphate disodium salt, recovered initiator, solvent

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91 Fly-Ash/Borosilicate Glass Based Geopolymers: A Mechanical and Microstructural Investigation

Authors: Gianmarco Taveri, Ivo Dlouhy

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Geopolymers are well-suited materials to abate CO2 emission coming from the Portland cement production, and then replace them, in the near future, in building and other applications. The cost of production of geopolymers may be seen the only weakness, but the use of wastes as raw materials could provide a valid solution to this problem, as demonstrated by the successful incorporation of fly-ash, a by-product of thermal power plants, and waste glasses. Recycled glass in waste-derived geopolymers was lately employed as a further silica source. In this work we present, for the first time, the introduction of recycled borosilicate glass (BSG). BSG is actually a waste glass, since it derives from dismantled pharmaceutical vials and cannot be reused in the manufacturing of the original articles. Owing to the specific chemical composition (BSG is an ‘alumino-boro-silicate’), it was conceived to provide the key components of zeolitic networks, such as amorphous silica and alumina, as well as boria (B2O3), which may replace Al2O3 and contribute to the polycondensation process. The solid–state MAS NMR spectroscopy was used to assess the extent of boron oxide incorporation in the structure of geopolymers, and to define the degree of networking. FTIR spectroscopy was utilized to define the degree of polymerization and to detect boron bond vibration into the structure. Mechanical performance was tested by means of 3 point bending (flexural strength), chevron notch test (fracture toughness), compression test (compressive strength), micro-indentation test (Vicker’s hardness). Spectroscopy (SEM and Confocal spectroscopy) was performed on the specimens conducted to failure. FTIR showed a characteristic absorption band attributed to the stretching modes of tetrahedral boron ions, whose tetrahedral configuration is compatible to the reaction product of geopolymerization. 27Al NMR and 29Si NMR spectra were instrumental in understanding the extent of the reaction. 11B NMR spectroscopies evidenced a change of the trigonal boron (BO3) inside the BSG in favor of a quasi-total tetrahedral boron configuration (BO4). Thanks to these results, it was inferred that boron is part of the geopolymeric structure, replacing the Si in the network, similarly to the aluminum, and therefore improving the quality of the microstructure, in favor of a more cross-linked network. As expected, the material gained as much as 25% in compressive strength (45 MPa) compared to the literature, whereas no improvements were detected in flexural strength (~ 5 MPa) and superficial hardness (~ 78 HV). The material also exhibited a low fracture toughness (0.35 MPa*m1/2), with a tangible brittleness. SEM micrographies corroborated this behavior, showing a ragged surface, along with several cracks, due to the high presence of porosity and impurities, acting as preferential points for crack initiation. The 3D pattern of the surface fracture, following the confocal spectroscopy, evidenced an irregular crack propagation, whose proclivity was mainly, but not always, to follow the porosity. Hence, the crack initiation and propagation are largely unpredictable.

Keywords: borosilicate glass, characterization, fly-ash, geopolymerization

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90 Expanded Polyurethane Foams and Waterborne-Polyurethanes from Vegetable Oils

Authors: A.Cifarelli, L. Boggioni, F. Bertini, L. Magon, M. Pitalieri, S. Losio

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Nowadays, the growing environmental awareness and the dwindling of fossil resources stimulate the polyurethane (PU) industry towards renewable polymers with low carbon footprint to replace the feed stocks from petroleum sources. The main challenge in this field consists in replacing high-performance products from fossil-fuel with novel synthetic polymers derived from 'green monomers'. The bio-polyols from plant oils have attracted significant industrial interest and major attention in scientific research due to their availability and biodegradability. Triglycerides rich in unsaturated fatty acids, such as soybean oil (SBO) and linseed oil (ELO), are particularly interesting because their structures and functionalities are tunable by chemical modification in order to obtain polymeric materials with expected final properties. Unfortunately, their use is still limited for processing or performance problems because a high functionality, as well as OH number of the polyols will result in an increase in cross-linking densities of the resulting PUs. The main aim of this study is to evaluate soy and linseed-based polyols as precursors to prepare prepolymers for the production of polyurethane foams (PUFs) or waterborne-polyurethanes (WPU) used as coatings. An effective reaction route is employed for its simplicity and economic impact. Indeed, bio-polyols were synthesized by a two-step method: epoxidation of the double bonds in vegetable oils and solvent-free ring-opening reaction of the oxirane with organic acids. No organic solvents have been used. Acids with different moieties (aliphatic or aromatics) and different length of hydrocarbon backbones can be used to customize polyols with different functionalities. The ring-opening reaction requires a fine tuning of the experimental conditions (time, temperature, molar ratio of carboxylic acid and epoxy group) to control the acidity value of end-product as well as the amount of residual starting materials. Besides, a Lewis base catalyst is used to favor the ring opening reaction of internal epoxy groups of the epoxidized oil and minimize the formation of cross-linked structures in order to achieve less viscous and more processable polyols with narrower polydispersity indices (molecular weight lower than 2000 g/mol⁻¹). The functionality of optimized polyols is tuned from 2 to 4 per molecule. The obtained polyols are characterized by means of GPC, NMR (¹H, ¹³C) and FT-IR spectroscopy to evaluate molecular masses, molecular mass distributions, microstructures and linkage pathways. Several polyurethane foams have been prepared by prepolymer method blending conventional synthetic polyols with new bio-polyols from soybean and linseed oils without using organic solvents. The compatibility of such bio-polyols with commercial polyols and diisocyanates is demonstrated. The influence of the bio-polyols on the foam morphology (cellular structure, interconnectivity), density, mechanical and thermal properties has been studied. Moreover, bio-based WPUs have been synthesized by well-established processing technology. In this synthesis, a portion of commercial polyols is substituted by the new bio-polyols and the properties of the coatings on leather substrates have been evaluated to determine coating hardness, abrasion resistance, impact resistance, gloss, chemical resistance, flammability, durability, and adhesive strength.

Keywords: bio-polyols, polyurethane foams, solvent free synthesis, waterborne-polyurethanes

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89 Knowledge and Practices on Waste Disposal Management Among Medical Technology Students at National University – Manila

Authors: John Peter Dacanay, Edison Ramos, Cristopher James Dicang

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Waste management is a global concern due to increasing waste production from changing consumption patterns and population growth. Proper waste disposal management is a critical aspect of public health and environmental protection. In the healthcare industry, medical waste is generated in large quantities, and if not disposed of properly, it poses a significant threat to human health and the environment. Efficient waste management conserves natural resources and prevents harm to human health, and implementing an effective waste management system can save human lives. The study aimed to assess the level of awareness and practices on waste disposal management, highlighting the understanding of proper disposal, potential hazards, and environmental implications among Medical Technology students. This would help to provide more recommendations for improving waste management practices in healthcare settings as well as for better waste management practices in educational institutions. From the collected data, a female of 21 years of age stands out among the respondents. With the frequency and percentage of medical technology students' knowledge of laboratory waste management being high, it indicates that all respondents demonstrated a solid understanding of proper disposal methods, regulations, risks, and handling procedures related to laboratory waste. That said, the findings emphasize the significance of education and awareness programs in equipping individuals involved in laboratory practices with the necessary knowledge to handle and dispose of hazardous and infectious waste properly. Most respondents demonstrate positive practices or are highly mannered in laboratory waste management, including proper segregation and disposal in designated containers. However, there are concerns about the occasional mixing of waste types, emphasizing the reiteration of proper waste segregation. Students show a strong commitment to using personal protective equipment and promptly cleaning up spills. Some students admit to improper disposal due to rushing, highlighting the importance of time management and safety prioritization. Overall, students follow protocols for hazardous waste disposal, indicating a responsible approach. The school's waste management system is perceived as adequate, but continuous assessment and improvement are necessary. Encouraging reporting of issues and concerns is crucial for ongoing improvement and risk mitigation. The analysis reveals a moderate positive relationship between the respondents' knowledge and practices regarding laboratory waste management. The statistically significant correlation with a p-value of 0.26 (p-value 0.05) suggests that individuals with higher levels of knowledge tend to exhibit better practices. These findings align with previous research emphasizing the pivotal role of knowledge in influencing individuals' behaviors and practices concerning laboratory waste management. When individuals possess a comprehensive understanding of proper procedures, regulations, and potential risks associated with laboratory waste, they are more inclined to adopt appropriate practices. Therefore, fostering knowledge through education and training is essential in promoting responsible and effective waste management in laboratory settings.

Keywords: waste disposal management, knowledge, attitude, practices

Procedia PDF Downloads 58
88 Population Diversity Studies in Dendrocalamus strictus Roxb. (Nees.) Through Morphological Parameters

Authors: Anugrah Tripathi, H. S. Ginwal, Charul Kainthola

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Bamboos are considered as valuable resources which have the potential of meeting current economic, environmental and social needs. Bamboo has played a key role in humankind and its livelihood since ancient time. Distributed in diverse areas across the globe, bamboo makes an important natural resource for hundreds of millions of people across the world. In some of the Asian countries and northeast part of India, bamboo is the basis of life on many horizons. India possesses the largest bamboo-bearing area across the world and a great extent of species richness, but this rich genetic resource and its diversity have dwindled in the natural forest due to forest fire, over exploitation, lack of proper management policies, and gregarious flowering behavior. Bamboos which are well known for their peculiar, extraordinary morphology, show a lot of variation in many scales. Among the various bamboo species, Dendrocalamus strictus is the most abundant bamboo resource in India, which is a deciduous, solid, and densely tufted bamboo. This species can thrive in wide gradients of geographical as well as climatic conditions. Due to this, it exhibits a significant amount of variation among the populations of different origins for numerous morphological features. Morphological parameters are the front-line criteria for the selection and improvement of any forestry species. Study on the diversity among eight important morphological characters of D. strictus was carried out, covering 16 populations from wide geographical locations of India following INBAR standards. Among studied 16 populations, three populations viz. DS06 (Gaya, Bihar), DS15 (Mirzapur, Uttar Pradesh), and DS16 (Bhogpur, Pinjore, Haryana) were found as superior populations with higher mean values for parametric characters (clump height, no. of culms/ clump, circumference of clump, internode diameter and internode length) and with the higher sum of ranks in non-parametric characters (straightness, disease, and pest incidence and branching pattern). All of these parameters showed an ample amount of variations among the studied populations and revealed a significant difference among the populations. Variation in morphological characters is very common in a species having wide distribution and is usually evident at various levels, viz., between and within the populations. They are of paramount importance for growth, biomass, and quick production gains. Present study also gives an idea for the selection of the population on the basis of these morphological parameters. From this study on morphological parameters and their variation, we may find an overview of best-performing populations for growth and biomass accumulation. Some of the studied parameters also provide ideas to standardize mechanisms of selecting and sustainable harvesting of the clumps by applying simpler silvicultural systems so that they can be properly managed in homestead gardens for the community utilization as well as by commercial growers to meet the requirement of industries and other stakeholders.

Keywords: Dendrocalamus strictus, homestead garden, gregarious flowering, stakeholders, INBAR

Procedia PDF Downloads 49
87 Photosynthesis Metabolism Affects Yield Potentials in Jatropha curcas L.: A Transcriptomic and Physiological Data Analysis

Authors: Nisha Govender, Siju Senan, Zeti-Azura Hussein, Wickneswari Ratnam

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Jatropha curcas, a well-described bioenergy crop has been extensively accepted as future fuel need especially in tropical regions. Ideal planting material required for large-scale plantation is still lacking. Breeding programmes for improved J. curcas varieties are rendered difficult due to limitations in genetic diversity. Using a combined transcriptome and physiological data, we investigated the molecular and physiological differences in high and low yielding Jatropha curcas to address plausible heritable variations underpinning these differences, in regard to photosynthesis, a key metabolism affecting yield potentials. A total of 6 individual Jatropha plant from 4 accessions described as high and low yielding planting materials were selected from the Experimental Plot A, Universiti Kebangsaan Malaysia (UKM), Bangi. The inflorescence and shoots were collected for transcriptome study. For the physiological study, each individual plant (n=10) from the high and low yielding populations were screened for agronomic traits, chlorophyll content and stomatal patterning. The J. curcas transcriptomes are available under BioProject PRJNA338924 and BioSample SAMN05827448-65, respectively Each transcriptome was subjected to functional annotation analysis of sequence datasets using the BLAST2Go suite; BLASTing, mapping, annotation, statistical analysis and visualization Large-scale phenotyping of the number of fruits per plant (NFPP) and fruits per inflorescence (FPI) classified the high yielding Jatropha accessions with average NFPP =60 and FPI > 10, whereas the low yielding accessions yielded an average NFPP=10 and FPI < 5. Next generation sequencing revealed genes with differential expressions in the high yielding Jatropha relative to the low yielding plants. Distinct differences were observed in transcript level associated to photosynthesis metabolism. DEGs collection in the low yielding population showed comparable CAM photosynthetic metabolism and photorespiration, evident as followings: phosphoenolpyruvate phosphate translocator chloroplastic like isoform with 2.5 fold change (FC) and malate dehydrogenase (2.03 FC). Green leaves have the most pronounced photosynthetic activity in a plant body due to significant accumulation of chloroplast. In most plants, the leaf is always the dominant photosynthesizing heart of the plant body. Large number of the DEGS in the high-yielding population were found attributable to chloroplast and chloroplast associated events; STAY-GREEN chloroplastic, Chlorophyllase-1-like (5.08 FC), beta-amylase (3.66 FC), chlorophyllase-chloroplastic-like (3.1 FC), thiamine thiazole chloroplastic like (2.8 FC), 1-4, alpha glucan branching enzyme chloroplastic amyliplastic (2.6FC), photosynthetic NDH subunit (2.1 FC) and protochlorophyllide chloroplastic (2 FC). The results were parallel to a significant increase in chlorophyll a content in the high yielding population. In addition to the chloroplast associated transcript abundance, the TOO MANY MOUTHS (TMM) at 2.9 FC, which code for distant stomatal distribution and patterning in the high-yielding population may explain high concentration of CO2. The results were in agreement with the role of TMM. Clustered stomata causes back diffusion in the presence of gaps localized closely to one another. We conclude that high yielding Jatropha population corresponds to a collective function of C3 metabolism with a low degree of CAM photosynthetic fixation. From the physiological descriptions, high chlorophyll a content and even distribution of stomata in the leaf contribute to better photosynthetic efficiency in the high yielding Jatropha compared to the low yielding population.

Keywords: chlorophyll, gene expression, genetic variation, stomata

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86 Solution Thermodynamics, Photophysical and Computational Studies of TACH2OX, a C-3 Symmetric 8-Hydroxyquinoline: Abiotic Siderophore Analogue of Enterobactin

Authors: B. K. Kanungo, Monika Thakur, Minati Baral

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8-hydroxyquinoline, (8HQ), experiences a renaissance due to its utility as a building block in metallosupramolecular chemistry and its versatile use of its derivatives in various fields of analytical chemistry, materials science, and pharmaceutics. It forms stable complexes with a variety of metal ions. Assembly of more than one such unit to form a polydentate chelator enhances its coordinating ability and the related properties due to the chelate effect resulting in high stability constant. Keeping in view the above, a nonadentate chelator N-[3,5-bis(8-hydroxyquinoline-2-amido)cyclohexyl]-8-hydroxyquinoline-2-carboxamide, (TACH2OX), containing a central cis,cis-1,3,5-triaminocyclohexane appended to three 8-hydroxyquinoline at 2-position through amide linkage is developed, and its solution thermodynamics, photophysical and Density Functional Theory (DFT) studies were undertaken. The synthesis of TACH2OX was carried out by condensation of cis,cis-1,3,5-triaminocyclohexane, (TACH) with 8‐hydroxyquinoline‐2‐carboxylic acid. The brown colored solid has been fully characterized through melting point, infrared, nuclear magnetic resonance, electrospray ionization mass and electronic spectroscopy. In solution, TACH2OX forms protonated complexes below pH 3.4, which consecutively deprotonates to generate trinegative ion with the rise of pH. Nine protonation constants for the ligand were obtained that ranges between 2.26 to 7.28. The interaction of the chelator with two trivalent metal ion Fe3+ and Al3+ were studied in aqueous solution at 298 K. The metal-ligand formation constants (ML) obtained by potentiometric and spectrophotometric method agree with each other. The protonated and hydrolyzed species were also detected in the system. The in-silico studies of the ligand, as well as the complexes including their protonated and deprotonated species assessed by density functional theory technique, gave an accurate correlation with each observed properties such as the protonation constants, stability constants, infra-red, nmr, electronic absorption and emission spectral bands. The nature of electronic and emission spectral bands in terms of number and type were ascertained from time-dependent density functional theory study and the natural transition orbitals (NTO). The global reactivity indices parameters were used for comparison of the reactivity of the ligand and the complex molecules. The natural bonding orbital (NBO) analysis could successfully describe the structure and bonding of the metal-ligand complexes specifying the percentage of contribution in atomic orbitals in the creation of molecular orbitals. The obtained high value of metal-ligand formation constants indicates that the newly synthesized chelator is a very powerful synthetic chelator. The minimum energy molecular modeling structure of the ligand suggests that the ligand, TACH2OX, in a tripodal fashion firmly coordinates to the metal ion as hexa-coordinated chelate displaying distorted octahedral geometry by binding through three sets of N, O- donor atoms, present in each pendant arm of the central tris-cyclohexaneamine tripod.

Keywords: complexes, DFT, formation constant, TACH2OX

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85 Multiparticulate SR Formulation of Dexketoprofen Trometamol by Wurster Coating Technique

Authors: Bhupendra G. Prajapati, Alpesh R. Patel

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The aim of this research work is to develop sustained release multi-particulates dosage form of Dexketoprofen trometamol, which is the pharmacologically active isomer of ketoprofen. The objective is to utilization of active enantiomer with minimal dose and administration frequency, extended release multi-particulates dosage form development for better patience compliance was explored. Drug loaded and sustained release coated pellets were prepared by fluidized bed coating principle by wurster coater. Microcrystalline cellulose as core pellets, povidone as binder and talc as anti-tacking agents were selected during drug loading while Kollicoat SR 30D as sustained release polymer, triethyl citrate as plasticizer and micronized talc as an anti-adherent were used in sustained release coating. Binder optimization trial in drug loading showed that there was increase in process efficiency with increase in the binder concentration. 5 and 7.5%w/w concentration of Povidone K30 with respect to drug amount gave more than 90% process efficiency while higher amount of rejects (agglomerates) were observed for drug layering trial batch taken with 7.5% binder. So for drug loading, optimum Povidone concentration was selected as 5% of drug substance quantity since this trial had good process feasibility and good adhesion of the drug onto the MCC pellets. 2% w/w concentration of talc with respect to total drug layering solid mass shows better anti-tacking property to remove unnecessary static charge as well as agglomeration generation during spraying process. Optimized drug loaded pellets were coated for sustained release coating from 16 to 28% w/w coating to get desired drug release profile and results suggested that 22% w/w coating weight gain is necessary to get the required drug release profile. Three critical process parameters of Wurster coating for sustained release were further statistically optimized for desired quality target product profile attributes like agglomerates formation, process efficiency, and drug release profile using central composite design (CCD) by Minitab software. Results show that derived design space consisting 1.0 to 1.2 bar atomization air pressure, 7.8 to 10.0 gm/min spray rate and 29-34°C product bed temperature gave pre-defined drug product quality attributes. Scanning Image microscopy study results were also dictate that optimized batch pellets had very narrow particle size distribution and smooth surface which were ideal properties for reproducible drug release profile. The study also focused on optimized dexketoprofen trometamol pellets formulation retain its quality attributes while administering with common vehicle, a liquid (water) or semisolid food (apple sauce). Conclusion: Sustained release multi-particulates were successfully developed for dexketoprofen trometamol which may be useful to improve acceptability and palatability of a dosage form for better patient compliance.

Keywords: dexketoprofen trometamol, pellets, fluid bed technology, central composite design

Procedia PDF Downloads 112
84 Biosurfactants Produced by Antarctic Bacteria with Hydrocarbon Cleaning Activity

Authors: Claudio Lamilla, Misael Riquelme, Victoria Saez, Fernanda Sepulveda, Monica Pavez, Leticia Barrientos

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Biosurfactants are compounds synthesized by microorganisms that show various chemical structures, including glycolipids, lipopeptides, polysaccharide-protein complex, phospholipids, and fatty acids. These molecules have attracted attention in recent years due to the amphipathic nature of these compounds, which allows their application in various activities related to emulsification, foaming, detergency, wetting, dispersion and solubilization of hydrophobic compounds. Microorganisms that produce biosurfactants are ubiquitous, not only present in water, soil, and sediments but in extreme conditions of pH, salinity or temperature such as those present in Antarctic ecosystems. Due to this, it is of interest to study biosurfactants producing bacterial strains isolated from Antarctic environments, with the potential to be used in various biotechnological processes. The objective of this research was to characterize biosurfactants produced by bacterial strains isolated from Antarctic environments, with potential use in biotechnological processes for the cleaning of sites contaminated with hydrocarbons. The samples were collected from soils and sediments in the South Shetland Islands and the Antarctic Peninsula, during the Antarctic Research Expedition INACH 2016, from both pristine and human occupied areas (influenced). The bacteria isolation was performed from solid R2A, M1 and LB media. The selection of strains producing biosurfactants was done by hemolysis test on blood agar plates (5%) and blue agar (CTAB). From 280 isolates, it was determined that 10 bacterial strains produced biosurfactants after stimulation with different carbon sources. 16S rDNA taxonomic markers, using the universal primers 27F-1492R, were used to identify these bacterias. Biosurfactants production was carried out in 250 ml flasks using Bushnell Hass liquid culture medium enriched with different carbon sources (olive oil, glucose, glycerol, and hexadecane) during seven days under constant stirring at 20°C. Each cell-free supernatant was characterized by physicochemical parameters including drop collapse, emulsification and oil displacement, as well as stability at different temperatures, salinity, and pH. In addition, the surface tension of each supernatant was quantified using a tensiometer. The strains with the highest activity were selected, and the production of biosurfactants was stimulated in six liters of culture medium. Biosurfactants were extracted from the supernatants with chloroform methanol (2:1). These biosurfactants were tested against crude oil and motor oil, to evaluate their displacement activity (detergency). The characterization by physicochemical properties of 10 supernatants showed that 80% of them produced the drop collapse, 60% had stability at different temperatures, and 90% had detergency activity in motor and olive oil. The biosurfactants obtained from two bacterial strains showed a high activity of dispersion of crude oil and motor oil with halos superior to 10 cm. We can conclude that bacteria isolated from Antarctic soils and sediments provide biological material of high quality for the production of biosurfactants, with potential applications in the biotechnological industry, especially in hydrocarbons -contaminated areas such as petroleum.

Keywords: antarctic, bacteria, biosurfactants, hydrocarbons

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83 Purple Spots on Historical Parchments: Confirming the Microbial Succession at the Basis of Biodeterioration

Authors: N. Perini, M. C. Thaller, F. Mercuri, S. Orlanducci, A. Rubechini, L. Migliore

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The preservation of cultural heritage is one of the major challenges of today’s society, because of the fundamental right of future generations to inherit it as the continuity with their historical and cultural identity. Parchments, consisting of a semi-solid matrix of collagen produced from animal skin (i.e., sheep or goats), are a significant part of the cultural heritage, being used as writing material for many centuries. Due to their animal origin, parchments easily undergo biodeterioration. The most common biological damage is characterized by isolated or coalescent purple spots that often leads to the detachment of the superficial layer and the loss of the written historical content of the document. Although many parchments with the same biodegradative features were analyzed, no common causative agent has been found so far. Very recently, a study was performed on a purple-damaged parchment roll dated back 1244 A.D, the A.A. Arm. I-XVIII 3328, belonging to the oldest collection of the Vatican Secret Archive (Fondo 'Archivum Arcis'), by comparing uncolored undamaged and purple damaged areas of the same document. As a whole, the study gave interesting results to hypothesize a model of biodeterioration, consisting of a microbial succession acting in two main phases: the first one, common to all the damaged parchments, is characterized by halophilic and halotolerant bacteria fostered by the salty environment within the parchment maybe induced by bringing of the hides; the second one, changing with the individual history of each parchment, determines the identity of its colonizers. The design of this model was pivotal to this study, performed by different labs of the Tor Vergata University (Rome, Italy), in collaboration with the Vatican Secret Archive. Three documents, belonging to a collection of dramatically damaged parchments archived as 'Faldone Patrizi A 19' (dated back XVII century A.D.), were analyzed through a multidisciplinary approach, including three updated technologies: (i) Next Generation Sequencing (NGS, Illumina) to describe the microbial communities colonizing the damaged and undamaged areas, (ii) RAMAN spectroscopy to analyze the purple pigments, (iii) Light Transmitted Analysis (LTA) to evaluate the kind and entity of the damage to native collagen. The metagenomic analysis obtained from NGS revealed DNA sequences belonging to Halobacterium salinarum mainly in the undamaged areas. RAMAN spectroscopy detected pigments within the purple spots, mainly bacteriorhodopsine/rhodopsin-like pigments, a purple transmembrane protein containing retinal and present in Halobacteria. The LTA technique revealed extremely damaged collagen structures in both damaged and undamaged areas of the parchments. In the light of these data, the study represents a first confirmation of the microbial succession model described above. The demonstration of this model is pivotal to start any possible new restoration strategy to bring back historical parchments to their original beauty, but also to open opportunities for intervention on a huge amount of documents.

Keywords: biodeterioration, parchments, purple spots, ecological succession

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82 Smart Laboratory for Clean Rivers in India - An Indo-Danish Collaboration

Authors: Nikhilesh Singh, Shishir Gaur, Anitha K. Sharma

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Climate change and anthropogenic stress have severely affected ecosystems all over the globe. Indian rivers are under immense pressure, facing challenges like pollution, encroachment, extreme fluctuation in the flow regime, local ignorance and lack of coordination between stakeholders. To counter all these issues a holistic river rejuvenation plan is needed that tests, innovates and implements sustainable solutions in the river space for sustainable river management. Smart Laboratory for Clean Rivers (SLCR) an Indo-Danish collaboration project, provides a living lab setup that brings all the stakeholders (government agencies, academic and industrial partners and locals) together to engage, learn, co-creating and experiment for a clean and sustainable river that last for ages. Just like every mega project requires piloting, SLCR has opted for a small catchment of the Varuna River, located in the Middle Ganga Basin in India. Considering the integrated approach of river rejuvenation, SLCR embraces various techniques and upgrades for rejuvenation. Likely, maintaining flow in the channel in the lean period, Managed Aquifer Recharge (MAR) is a proven technology. In SLCR, Floa-TEM high-resolution lithological data is used in MAR models to have better decision-making for MAR structures nearby of the river to enhance the river aquifer exchanges. Furthermore, the concerns of quality in the river are a big issue. A city like Varanasi which is located in the last stretch of the river, generates almost 260 MLD of domestic waste in the catchment. The existing STP system is working at full efficiency. Instead of installing a new STP for the future, SLCR is upgrading those STPs with an IoT-based system that optimizes according to the nutrient load and energy consumption. SLCR also advocate nature-based solutions like a reed bed for the drains having less flow. In search of micropollutants, SLCR uses fingerprint analysis involves employing advanced techniques like chromatography and mass spectrometry to create unique chemical profiles. However, rejuvenation attempts cannot be possible without involving the entire catchment. A holistic water management plan that includes storm management, water harvesting structure to efficiently manage the flow of water in the catchment and installation of several buffer zones to restrict pollutants entering into the river. Similarly, carbon (emission and sequestration) is also an important parameter for the catchment. By adopting eco-friendly practices, a ripple effect positively influences the catchment's water dynamics and aids in the revival of river systems. SLCR has adopted 4 villages to make them carbon-neutral and water-positive. Moreover, for the 24×7 monitoring of the river and the catchment, robust IoT devices are going to be installed to observe, river and groundwater quality, groundwater level, river discharge and carbon emission in the catchment and ultimately provide fuel for the data analytics. In its completion, SLCR will provide a river restoration manual, which will strategise the detailed plan and way of implementation for stakeholders. Lastly, the entire process is planned in such a way that will be managed by local administrations and stakeholders equipped with capacity-building activity. This holistic approach makes SLCR unique in the field of river rejuvenation.

Keywords: sustainable management, holistic approach, living lab, integrated river management

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81 Environmental Management Accounting Practices and Policies within the Higher Education Sector: An Exploratory Study of the University of KwaZulu Natal

Authors: Kiran Baldavoo, Mishelle Doorasamy

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Universities have a role to play in the preservation of the environment, and the study attempted to evaluate the environmental management accounting (EMA) processes at UKZN. UKZN, a South African university, generates the same direct and indirect environmental impacts as the higher education sector worldwide. This is significant within the context of the South African environment which is constantly plagued by having to effectively manage the already scarce resources of water and energy, evident through the imposition of water and energy restrictions over the recent years. The study’s aim is to increase awareness of having a structured approach to environmental management in order to achieve the strategic environmental goals of the university. The research studied the experiences of key managers within UKZN, with the purpose of exploring the potential factors which influence the decision to adopt and apply EMA within the higher education sector. The study comprised two objectives, namely understanding the current state of accounting practices for managing major environmental costs and identifying factors influencing EMA adoption within the university. The study adopted a case study approach, comprising semi-structured interviews of key personnel involved in Management Accounting, Environmental Management, and Academic Schools within the university. Content analysis was performed on the transcribed interview data. A Theoretical Framework derived from literature was adopted to guide data collection and focus the study. Contingency and Institutional theory was the resultant basis of the derived framework. The findings of the first objective revealed that there was a distinct lack of EMA utilization within the university. There was no distinct policy on EMA, resulting in minimal environmental cost information being brought to the attention of senior management. The university embraced the principles of environmental sustainability; however, efforts to improve internal environmental accountability primarily from an accounting perspective was absent. The findings of the second objective revealed that five key barriers contributed to the lack of EMA utilization within the university. The barriers being attitudinal, informational, institutional, technological, and lack of incentives (financial). The results and findings of this study supported the use and application of EMA within the higher education sector. Participants concurred that EMA was underutilized and if implemented, would realize significant benefits for both the university and environment. Environmental management accounting is being widely acknowledged as a key management tool that can facilitate improved financial and environmental performance via the concept of enhanced environmental accountability. Historically research has been concentrated primarily on the manufacturing industry, due to it generating the greatest proportion of environmental impacts. Service industries are also an integral component of environmental management as they contribute significant environmental impacts, both direct and indirect. Educational institutions such as universities form part of the service sector and directly impact on the environment through the consumption of paper, energy, and water and solid waste generated, with the associated demands.

Keywords: environmental management accounting, environmental impacts, higher education, Southern Africa

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80 Li-Ion Batteries vs. Synthetic Natural Gas: A Life Cycle Analysis Study on Sustainable Mobility

Authors: Guido Lorenzi, Massimo Santarelli, Carlos Augusto Santos Silva

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The growth of non-dispatchable renewable energy sources in the European electricity generation mix is promoting the research of technically feasible and cost-effective solutions to make use of the excess energy, produced when the demand is low. The increasing intermittent renewable capacity is becoming a challenge to face especially in Europe, where some countries have shares of wind and solar on the total electricity produced in 2015 higher than 20%, with Denmark around 40%. However, other consumption sectors (mainly transportation) are still considerably relying on fossil fuels, with a slow transition to other forms of energy. Among the opportunities for different mobility concepts, electric (EV) and biofuel-powered vehicles (BPV) are the options that currently appear more promising. The EVs are targeting mainly the light duty users because of their zero (Full electric) or reduced (Hybrid) local emissions, while the BPVs encourage the use of alternative resources with the same technologies (thermal engines) used so far. The batteries which are applied to EVs are based on ions of Lithium because of their overall good performance in energy density, safety, cost and temperature performance. Biofuels, instead, can be various and the major difference is in their physical state (liquid or gaseous). In this study gaseous biofuels are considered and, more specifically, Synthetic Natural Gas (SNG) produced through a process of Power-to-Gas consisting in an electrochemical upgrade (with Solid Oxide Electrolyzers) of biogas with CO2 recycling. The latter process combines a first stage of electrolysis, where syngas is produced, and a second stage of methanation in which the product gas is turned into methane and then made available for consumption. A techno-economic comparison between the two alternatives is possible, but it does not capture all the different aspects involved in the two routes for the promotion of a more sustainable mobility. For this reason, a more comprehensive methodology, i.e. Life Cycle Assessment, is adopted to describe the environmental implications of using excess electricity (directly or indirectly) for new vehicle fleets. The functional unit of the study is 1 km and the two options are compared in terms of overall CO2 emissions, both considering Cradle to Gate and Cradle to Grave boundaries. Showing how production and disposal of materials affect the environmental performance of the analyzed routes is useful to broaden the perspective on the impacts that different technologies produce, in addition to what is emitted during the operational life. In particular, this applies to batteries for which the decommissioning phase has a larger impact on the environmental balance compared to electrolyzers. The lower (more than one order of magnitude) energy density of Li-ion batteries compared to SNG implies that for the same amount of energy used, more material resources are needed to obtain the same effect. The comparison is performed in an energy system that simulates the Western European one, in order to assess which of the two solutions is more suitable to lead the de-fossilization of the transport sector with the least resource depletion and the mildest consequences for the ecosystem.

Keywords: electrical energy storage, electric vehicles, power-to-gas, life cycle assessment

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79 Biomimetic Dinitrosyl Iron Complexes: A Synthetic, Structural, and Spectroscopic Study

Authors: Lijuan Li

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Nitric oxide (NO) has become a fascinating entity in biological chemistry over the past few years. It is a gaseous lipophilic radical molecule that plays important roles in several physiological and pathophysiological processes in mammals, including activating the immune response, serving as a neurotransmitter, regulating the cardiovascular system, and acting as an endothelium-derived relaxing factor. NO functions in eukaryotes both as a signal molecule at nanomolar concentrations and as a cytotoxic agent at micromolar concentrations. The latter arises from the ability of NO to react readily with a variety of cellular targets leading to thiol S-nitrosation, amino acid N-nitrosation, and nitrosative DNA damage. Nitric oxide can readily bind to metals to give metal-nitrosyl (M-NO) complexes. Some of these species are known to play roles in biological NO storage and transport. These complexes have different biological, photochemical, or spectroscopic properties due to distinctive structural features. These recent discoveries have spawned a great interest in the development of transition metal complexes containing NO, particularly its iron complexes that are central to the role of nitric oxide in the body. Spectroscopic evidence would appear to implicate species of “Fe(NO)2+” type in a variety of processes ranging from polymerization, carcinogenesis, to nitric oxide stores. Our research focuses on isolation and structural studies of non-heme iron nitrosyls that mimic biologically active compounds and can potentially be used for anticancer drug therapy. We have shown that reactions between Fe(NO)2(CO)2 and a series of imidazoles generated new non-heme iron nitrosyls of the form Fe(NO)2(L)2 [L = imidazole, 1-methylimidazole, 4-methylimidazole, benzimidazole, 5,6-dimethylbenzimidazole, and L-histidine] and a tetrameric cluster of [Fe(NO)2(L)]4 (L=Im, 4-MeIm, BzIm, and Me2BzIm), resulted from the interactions of Fe(NO)2 with a series of substituted imidazoles was prepared. Recently, a series of sulfur bridged iron di nitrosyl complexes with the general formula of [Fe(µ-RS)(NO)2]2 (R = n-Pr, t-Bu, 6-methyl-2-pyridyl, and 4,6-dimethyl-2-pyrimidyl), were synthesized by the reaction of Fe(NO)2(CO)2 with thiols or thiolates. Their structures and properties were studied by IR, UV-vis, 1H-NMR, EPR, electrochemistry, X-ray diffraction analysis and DFT calculations. IR spectra of these complexes display one weak and two strong NO stretching frequencies (νNO) in solution, but only two strong νNO in solid. DFT calculations suggest that two spatial isomers of these complexes bear 3 Kcal energy difference in solution. The paramagnetic complexes [Fe2(µ-RS)2(NO)4]-, have also been investigated by EPR spectroscopy. Interestingly, the EPR spectra of complexes exhibit an isotropic signal of g = 1.998 - 2.004 without hyperfine splitting. The observations are consistent with the results of calculations, which reveal that the unpaired electron dominantly delocalize over the two sulfur and two iron atoms. The difference of the g values between the reduced form of iron-sulfur clusters and the typical monomeric di nitrosyl iron complexes is explained, for the first time, by of the difference in unpaired electron distributions between the two types of complexes, which provides the theoretical basis for the use of g value as a spectroscopic tool to differentiate these biologically active complexes.

Keywords: di nitrosyl iron complex, metal nitrosyl, non-heme iron, nitric oxide

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78 The Temperature Degradation Process of Siloxane Polymeric Coatings

Authors: Andrzej Szewczak

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Study of the effect of high temperatures on polymer coatings represents an important field of research of their properties. Polymers, as materials with numerous features (chemical resistance, ease of processing and recycling, corrosion resistance, low density and weight) are currently the most widely used modern building materials, among others in the resin concrete, plastic parts, and hydrophobic coatings. Unfortunately, the polymers have also disadvantages, one of which decides about their usage - low resistance to high temperatures and brittleness. This applies in particular thin and flexible polymeric coatings applied to other materials, such a steel and concrete, which degrade under varying thermal conditions. Research about improvement of this state includes methods of modification of the polymer composition, structure, conditioning conditions, and the polymerization reaction. At present, ways are sought to reflect the actual environmental conditions, in which the coating will be operating after it has been applied to other material. These studies are difficult because of the need for adopting a proper model of the polymer operation and the determination of phenomena occurring at the time of temperature fluctuations. For this reason, alternative methods are being developed, taking into account the rapid modeling and the simulation of the actual operating conditions of polymeric coating’s materials in real conditions. The nature of a duration is typical for the temperature influence in the environment. Studies typically involve the measurement of variation one or more physical and mechanical properties of such coating in time. Based on these results it is possible to determine the effects of temperature loading and develop methods affecting in the improvement of coatings’ properties. This paper contains a description of the stability studies of silicone coatings deposited on the surface of a ceramic brick. The brick’s surface was hydrophobized by two types of inorganic polymers: nano-polymer preparation based on dialkyl siloxanes (Series 1 - 5) and an aqueous solution of the silicon (series 6 - 10). In order to enhance the stability of the film formed on the brick’s surface and immunize it to variable temperature and humidity loading, the nano silica was added to the polymer. The right combination of the polymer liquid phase and the solid phase of nano silica was obtained by disintegration of the mixture by the sonification. The changes of viscosity and surface tension of polymers were defined, which are the basic rheological parameters affecting the state and the durability of the polymer coating. The coatings created on the brick’s surfaces were then subjected to a temperature loading of 100° C and moisture by total immersion in water, in order to determine any water absorption changes caused by damages and the degradation of the polymer film. The effect of moisture and temperature was determined by measurement (at specified number of cycles) of changes in the surface hardness (using a Vickers’ method) and the absorption of individual samples. As a result, on the basis of the obtained results, the degradation process of polymer coatings related to their durability changes in time was determined.

Keywords: silicones, siloxanes, surface hardness, temperature, water absorption

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77 Interactively Developed Capabilities for Environmental Management Systems: An Exploratory Investigation of SMEs

Authors: Zhuang Ma, Zihan Zhang, Yu Li

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Environmental concerns from stakeholders (e.g., governments & customers) have pushed firms to integrate environmental management systems into business processes such as R&D, manufacturing, and marketing. Environmental systems include managing environmental risks and pollution control (e.g., air pollution control, waste-water treatment, noise control, energy recycling & solid waste treatment) through raw material management, the elimination and reduction of contaminants, recycling, and reuse in firms' operational processes. Despite increasing studies on firms' proactive adoption of environmental management, their focus is primarily on large corporations operating in developed economies. Investigations in the environmental management efforts of small and medium-sized enterprises (SMEs) are scarce. This is problematic for SMEs because, unlike large corporations, SMEs have limited awareness, resources, capabilities to adapt their operational routines to address environmental impacts. The purpose of this study is to explore how SMEs develop organizational capabilities through interactions with business partners (e.g., environmental management specialists & customers). Drawing on the resource-based view (RBV) and an organizational capabilities perspective, this study investigates the interactively developed capabilities that allow SMEs to adopt environmental management systems. Using an exploratory approach, the study includes 12 semi-structured interviews with senior managers from four SMEs, two environmental management specialists, and two customers in the pharmaceutical sector in Chongqing, China. Findings of this study include four key organizational capabilities: 1) ‘dynamic marketing’ capability, which allows SMEs to recoup the investments in environmental management systems by developing environmentally friendly products to address customers' ever-changing needs; 2) ‘process improvement’ capability, which allows SMEs to select and adopt the latest technologies from biology, chemistry, new material, and new energy sectors into the production system for improved environmental performance and cost-reductions; and 3) ‘relationship management’ capability which allows SMEs to improve corporate image among the public, social media, government agencies, and customers, who in turn help SMEs to overcome their competitive disadvantages. These interactively developed capabilities help SMEs to address larger competitors' foothold in the local market, reduce market constraints, and exploit competitive advantages in other regions (e.g., Guangdong & Jiangsu) of China. These findings extend the RBV and organizational capabilities perspective; that is, SMEs can develop the essential resources and capabilities required for environmental management through interactions with upstream and downstream business partners. While a limited number of studies did highlight the importance of interactions among SMEs, customers, suppliers, NGOs, industrial associations, and consulting firms, they failed to explore the specific capabilities developed through these interactions. Additionally, the findings can explain how a proactive adoption of environmental management systems could help some SMEs to overcome the institutional and market restraints on their products, thereby springboarding into larger, more environmentally demanding, yet more profitable markets compared with their existing market.

Keywords: capabilities, environmental management systems, interactions, SMEs

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