Search results for: black sand mineral

Authors: Lynette Lincoln, Sunil S. More

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With the rising demand of sugar used today, it is proposed that world sugar is expected to escalate up to 203 million tonnes by 2021. Hydrolysis of sucrose (table sugar) into glucose and fructose equimolar mixture is catalyzed by β-D-fructofuranoside fructohydrolase (EC 3.2.1.26), commonly called as invertase. For fluid filled center in chocolates, preparation of artificial honey, as a sweetener and especially to ensure that food stuffs remain fresh, moist and soft for longer spans invertase is applied widely and is extensively being used. From an industrial perspective, properties such as increased solubility, osmotic pressure and prevention of crystallization of sugar in food products are highly desired. Screening for invertase does not involve plate assay/qualitative test to determine the enzyme production. In this study, we use a three-step screening strategy for identification of a novel bacterial isolate from soil which is positive for invertase production. The primary step was serial dilution of soil collected from sugarcane fields (black soil, Maddur region of Mandya district, Karnataka, India) was grown on a Czapek-Dox medium (pH 5.0) containing sucrose as the sole C-source. Only colonies with the capability to utilize/breakdown sucrose exhibited growth. Bacterial isolates released invertase in order to take up sucrose, splitting the disaccharide into simple sugars. Secondly, invertase activity was determined from cell free extract by measuring the glucose released in the medium at 540 nm. Morphological observation of the most potent bacteria was examined by several identification tests using Bergey’s manual, which enabled us to know the genus of the isolate to be Bacillus. Furthermore, this potent bacterial colony was subjected to 16S rDNA PCR amplification and a single discrete PCR amplicon band of 1500 bp was observed. The 16S rDNA sequence was used to carry out BLAST alignment search tool of NCBI Genbank database to obtain maximum identity score of sequence. Molecular sequencing and identification was performed by Xcelris Labs Ltd. (Ahmedabad, India). The colony was identified as Bacillus sp. BAB-3434, indicating to be the first novel strain for extracellular invertase production. Molasses, a by-product of the sugarcane industry is a dark viscous liquid obtained upon crystallization of sugar. An enhanced invertase production and optimization studies were carried out by one-factor-at-a-time approach. Crucial parameters such as time course (24 h), pH (6.0), temperature (45 °C), inoculum size (2% v/v), N-source (yeast extract, 0.2% w/v) and C-source (molasses, 4% v/v) were found to be optimum demonstrating an increased yield. The findings of this study reveal a simple screening method of an extracellular invertase from a rapidly growing Bacillus sp., and selection of best factors that elevate enzyme activity especially utilization of molasses which served as an ideal substrate and also as C-source, results in a cost-effective production under submerged conditions. The invert mixture could be a replacement for table sugar which is an economic advantage and reduce the tedious work of sugar growers. On-going studies involve purification of extracellular invertase and determination of transfructosylating activity as at high concentration of sucrose, invertase produces fructooligosaccharides (FOS) which possesses probiotic properties.

Keywords: Bacillus sp., invertase, molasses, screening, submerged fermentation

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Authors: Abderrazak Bannari

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Acid Mine Drainage (AMD) from mine wastes and contaminations of soils and water with metals are considered as a major environmental problem in mining areas. It is produced by interactions of water, air, and sulphidic mine wastes. This environment problem results from a series of chemical and biochemical oxidation reactions of sulfide minerals e.g. pyrite and pyrrhotite. These reactions lead to acidity as well as the dissolution of toxic and heavy metals (Fe, Mn, Cu, etc.) from tailings waste rock piles, and open pits. Soil and aquatic ecosystems could be contaminated and, consequently, human health and wildlife will be affected. Furthermore, secondary minerals, typically formed during weathering of mine waste storage areas when the concentration of soluble constituents exceeds the corresponding solubility product, are also important. The most common secondary mineral compositions are hydrous iron oxide (goethite, etc.) and hydrated iron sulfate (jarosite, etc.). The objectives of this study focus on the detection and mapping of MIOP in the soil using Hyperion EO-1 (Earth Observing - 1) hyperspectral data and constrained linear spectral mixture analysis (CLSMA) algorithm. The abandoned Kettara mine, located approximately 35 km northwest of Marrakech city (Morocco) was chosen as study area. During 44 years (from 1938 to 1981) this mine was exploited for iron oxide and iron sulphide minerals. Previous studies have shown that Kettara surrounding soils are contaminated by heavy metals (Fe, Cu, etc.) as well as by secondary minerals. To achieve our objectives, several soil samples representing different MIOP classes have been resampled and located using accurate GPS ( ≤ ± 30 cm). Then, endmembers spectra were acquired over each sample using an Analytical Spectral Device (ASD) covering the spectral domain from 350 to 2500 nm. Considering each soil sample separately, the average of forty spectra was resampled and convolved using Gaussian response profiles to match the bandwidths and the band centers of the Hyperion sensor. Moreover, the MIOP content in each sample was estimated by geochemical analyses in the laboratory, and a ground truth map was generated using simple Kriging in GIS environment for validation purposes. The acquired and used Hyperion data were corrected for a spatial shift between the VNIR and SWIR detectors, striping, dead column, noise, and gain and offset errors. Then, atmospherically corrected using the MODTRAN 4.2 radiative transfer code, and transformed to surface reflectance, corrected for sensor smile (1-3 nm shift in VNIR and SWIR), and post-processed to remove residual errors. Finally, geometric distortions and relief displacement effects were corrected using a digital elevation model. The MIOP fraction map was extracted using CLSMA considering the entire spectral range (427-2355 nm), and validated by reference to the ground truth map generated by Kriging. The obtained results show the promising potential of the proposed methodology for the detection and mapping of mine iron oxide pollution in the soil.

Keywords: hyperion eo-1, hyperspectral, mine iron oxide pollution, environmental impact, unmixing

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Authors: Edward Shizha, Edward Makwarimba

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Newcomer and refugee youth feel excluded in the education system in Canada, and the formal education environment does not fully cater for their learning needs. The objective of this study was to build knowledge and understanding of the educational needs and experiences of these youth in Canada and how available afterschool programs can most effectively support their learning needs and academic outcomes. The Employment and Social Development Canada (ESDC), which funded this research, enables and empowers students to advance their educational experience through targeted investments in services that are delivered by youth-serving organizations outside the formal education system through afterschool initiatives. A literature review and a provincial/territorial internet scan were conducted to determine the availability of services and programs that serve the educational needs and academic outcomes of newcomer youth in 10 provinces and 3 territories in Canada. The goal was to identify intersectional factors (e.g., gender, sexuality, culture, social class, race, etc.) that influence educational outcomes of newcomer/refugee students and to recommend ways the ESDC could complement settlement services to enhance students’ educational success. First, data was collected through a literature search of various databases, including PubMed, Web of Science, Scopus, Google docs, ACADEMIA, and grey literature, including government documents, to inform our analysis. Second, a provincial/territorial internet scan was conducted using a template that was created by ESDC staff with the input of the researchers. The objective of the web-search scan was to identify afterschool programs, projects, and initiatives offered to newcomer/refugee youth by service provider organizations. The method for the scan included both qualitative and quantitative data gathering. Both the literature review and the provincial/territorial scan revealed that there are gender disparities in educational outcomes of newcomer and refugee youth. High school completion rates by gender show that boys are at higher risk of not graduating than girls and that girls are more likely than boys to have at least a high school diploma and more likely to proceed to postsecondary education. Findings from literature reveal that afterschool programs are required for refugee youth who experience mental health challenges and miss out on significant periods of schooling, which affect attendance, participation, and graduation from high school. However, some refugee youth use their resilience and ambition to succeed in their educational outcomes. Another finding showed that some immigrant/refugee students, through ethnic organizations and familial affiliation, maintain aspects of their cultural values, parental expectations and ambitious expectations for their own careers to succeed in both high school and postsecondary education. The study found a significant combination of afterschool programs that include academic support, scholarships, bursaries, homework support, career readiness, internships, mentorship, tutoring, non-clinical counselling, mental health and social well-being support, language skills, volunteering opportunities, community connections, peer networking, culturally relevant services etc. These programs assist newcomer youth to develop self-confidence and prepare for academic success and future career development. The study concluded that advantages of afterschool programs are greatest for youth at risk for poor educational outcomes, such as Latino and Black youth, including 2SLGBTQI+ immigrant youth.

Keywords: afterschool programs, educational outcomes, newcomer youth, refugee youth, youth-serving organizations

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Authors: Susana Barreto

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This paper explores a pedagogical exercise that employs family photos as catalysts for teaching visual analysis and inspiring academic writing among MA students. The study aimed to achieve two primary objectives: to impart students with the skills of analyzing images or artifacts and to ignite their writing for research purposes. Conducted at Viana Polytechnic in Portugal, the exercise involved two classes on Arts Management and Art Education Master course comprising approximately twenty students from diverse academic backgrounds, including Economics, Design, Fine Arts, and Sociology, among others. The exploratory exercise involved selecting an old family photo, analyzing its content and context, and deconstructing the chosen images in an intuitive and systematic manner. Students were encouraged to engage in photo elicitation, seeking insights from family/friends to gain multigenerational perspectives on the images. The feedback received from this exercise was consistently positive, largely due to the personal connection students felt with the objects of analysis. Family photos, with their emotional significance, fostered deeper engagement and motivation in the learning process. Furthermore, visual analysing family photos stimulated critical thinking as students interpreted the composition, subject matter, and potential meanings embedded in the images. This practice enhanced their ability to comprehend complex visual representations and construct compelling visual narratives, thereby facilitating the writing process. The exercise also facilitated the identification of patterns, similarities, and differences by comparing different family photos, leading to a more comprehensive analysis of visual elements and themes. Throughout the exercise, students found analyzing their own photographs both enjoyable and insightful. They progressed through preliminary analysis, explored content and context, and artfully interwove these components. Additionally, students experimented with various techniques such as converting photos to black and white, altering framing angles, and adjusting sizes to unveil hidden meanings.The methodology employed included observation, documental analysis of written reports, and student interviews. By including students from diverse academic backgrounds, the study enhanced its external validity, enabling a broader range of perspectives and insights during the exercise. Furthermore, encouraging students to seek multigenerational perspectives from family and friends added depth to the analysis, enriching the learning experience and broadening the understanding of the cultural and historical context associated with the family photos Highlighting the emotional significance of these family photos and the personal connection students felt with the objects of analysis fosters a deeper connection to the subject matter. Moreover, the emphasis on stimulating critical thinking through the analysis of composition, subject matter, and potential meanings in family photos suggests a targeted approach to developing analytical skills. This improvement focuses specifically on critical thinking and visual analysis, enhancing the overall quality of the exercise. Additionally, the inclusion of a step where students compare different family photos to identify patterns, similarities, and differences further enhances the depth of the analysis. This comparative approach adds a layer of complexity to the exercise, ultimately leading to a more comprehensive understanding of visual elements and themes. The expected results of this study will culminate in a set of practical recommendations for implementing this exercise in academic settings.

Keywords: visual analysis, academic writing, pedagogical exercise, family photos

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Authors: Francisco J. Ortega, Claudia Roman, Moisés García-Morales, Francisco J. Navarro

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Asphaltic bitumen has been largely used in both industrial and civil engineering, mostly in pavement construction and roofing membrane manufacture. However, bitumen as such is greatly susceptible to temperature variations, and dramatically changes its in-service behavior from a viscoelastic liquid, at medium-high temperatures, to a brittle solid at low temperatures. Bitumen modification prevents these problems and imparts improved performance. Isocyanates like polymeric MDI (mixture of 4,4′-diphenylmethane di-isocyanate, 2,4’ and 2,2’ isomers, and higher homologues) have shown to remarkably enhance bitumen properties at the highest in-service temperatures expected. This comes from the reaction between the –NCO pendant groups of the oligomer and the most polar groups of asphaltenes and resins in bitumen. In addition, oxygen diffusion and/or UV radiation may provoke bitumen hardening and ageing. With the purpose of minimizing these effects, nano-layered-silicates (nanoclays) are increasingly being added to bitumen formulations. Montmorillonites, a type of naturally occurring mineral, may produce a nanometer scale dispersion which improves bitumen thermal, mechanical and barrier properties. In order to increase their lipophilicity, these nanoclays are normally treated so that organic cations substitute the inorganic cations located in their intergallery spacing. In the present work, the combined effect of polymeric MDI and the commercial montmorillonite Cloisite® 20A was evaluated. A selected bitumen with penetration within the range 160/220 was modified with 10 wt.% Cloisite® 20A and 2 wt.% polymeric MDI, and the resulting ternary composites were characterized by linear rheology, X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). The rheological tests evidenced a notable solid-like behavior at the highest temperatures studied when bitumen was just loaded with 10 wt.% Cloisite® 20A and high-shear blended for 20 minutes. However, if polymeric MDI was involved, the sequence of addition exerted a decisive control on the linear rheology of the final ternary composites. Hence, in bitumen/Cloisite® 20A/polymeric MDI formulations, the previous solid-like behavior disappeared. By contrast, an inversion in the order of addition (bitumen/polymeric MDI/ Cloisite® 20A) enhanced further the solid-like behavior imparted by the nanoclay. In order to gain a better understanding of the factors that govern the linear rheology of these ternary composites, a morphological and microstructural characterization based on XRD and AFM was conducted. XRD demonstrated the existence of clay stacks intercalated by bitumen molecules to some degree. However, the XRD technique cannot provide detailed information on the extent of nanoclay delamination, unless the entire fraction has effectively been fully delaminated (situation in which no peak is observed). Furthermore, XRD was unable to provide precise knowledge neither about the spatial distribution of the intercalated/exfoliated platelets nor about the presence of other structures at larger length scales. In contrast, AFM proved its power at providing conclusive information on the morphology of the composites at the nanometer scale and at revealing the structural modification that yielded the rheological properties observed. It was concluded that high-shear blending brought about a nanoclay-reinforced network. As for the bitumen/Cloisite® 20A/polymeric MDI formulations, the solid-like behavior was destroyed as a result of the agglomeration of the nanoclay platelets promoted by chemical reactions.

Keywords: Atomic Force Microscopy, bitumen, composite, isocyanate, montmorillonite.

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Authors: Diogo José Morgado Rebelo, Francisco António Carneiro Pacheco de Andrade, Paulo Jorge Freitas de Oliveira Novais

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Not everything in AI-power consumer credit scoring turns out to be a wonder. When using AI in Creditworthiness Assessment (CWA), opacity and unfairness ‘sins’ must be considered to the task be deemed Responsible. AI software is not always 100% accurate, which can lead to misclassification. Discrimination of some groups can be exponentiated. A hetero personalized identity can be imposed on the individual(s) affected. Also, autonomous CWA sometimes lacks transparency when using black box models. However, for this intended purpose, human analysts ‘on-the-loop’ might not be the best remedy consumers are looking for in credit. This study seeks to explore the legality of implementing a Multi-Agent System (MAS) framework in consumer CWA to ensure compliance with the regulation outlined in Article 14(4) of the Proposal for an Artificial Intelligence Act (AIA), dated 21 April 2021 (as per the last corrigendum by the European Parliament on 19 April 2024), Especially with the adoption of Art. 18(8)(9) of the EU Directive 2023/2225, of 18 October, which will go into effect on 20 November 2026, there should be more emphasis on the need for hybrid oversight in AI-driven scoring to ensure fairness and transparency. In fact, the range of EU regulations on AI-based consumer credit will soon impact the AI lending industry locally and globally, as shown by the broad territorial scope of AIA’s Art. 2. Consequently, engineering the law of consumer’s CWA is imperative. Generally, the proposed MAS framework consists of several layers arranged in a specific sequence, as follows: firstly, the Data Layer gathers legitimate predictor sets from traditional sources; then, the Decision Support System Layer, whose Neural Network model is trained using k-fold Cross Validation, provides recommendations based on the feeder data; the eXplainability (XAI) multi-structure comprises Three-Step-Agents; and, lastly, the Oversight Layer has a 'Bottom Stop' for analysts to intervene in a timely manner. From the analysis, one can assure a vital component of this software is the XAY layer. It appears as a transparent curtain covering the AI’s decision-making process, enabling comprehension, reflection, and further feasible oversight. Local Interpretable Model-agnostic Explanations (LIME) might act as a pillar by offering counterfactual insights. SHapley Additive exPlanation (SHAP), another agent in the XAI layer, could address potential discrimination issues, identifying the contribution of each feature to the prediction. Alternatively, for thin or no file consumers, the Suggestion Agent can promote financial inclusion. It uses lawful alternative sources such as the share of wallet, among others, to search for more advantageous solutions to incomplete evaluation appraisals based on genetic programming. Overall, this research aspires to bring the concept of Machine-Centered Anthropocentrism to the table of EU policymaking. It acknowledges that, when put into service, credit analysts no longer exert full control over the data-driven entities programmers have given ‘birth’ to. With similar explanatory agents under supervision, AI itself can become self-accountable, prioritizing human concerns and values. AI decisions should not be vilified inherently. The issue lies in how they are integrated into decision-making and whether they align with non-discrimination principles and transparency rules.

Keywords: creditworthiness assessment, hybrid oversight, machine-centered anthropocentrism, EU policymaking

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Authors: Irakli Gamkrelidze, David Shengelia, Giorgi Chichinadze, Tamara Tsutsunava, Giorgi Beridze, Tamara Tsamalashvili, Ketevan Tedliashvili, Irakli Javakhishvili

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The Caucasus is situated between the Eurasian and Africa-Arabian plates and represents a component of the Mediterranean (Alpine-Himalayan) collision belt. The Loki crystalline massif crops out within one of the terranes of the Caucasus – Baiburt-Sevanian terrane. By the end of 2018, a digital geological map (1:50 000) of the Loki massif was compiled. The presented map is of great importance for the region since there is no large-scale geological map which reflects the present standards of the geological study of the massif up to the last time. The existing State Geological Map of the Loki massif is very outdated. A new map drown by using GIS (Geographic Information System) technology is loaded with multi-informative details that include: specified contours of geological units and separate tectonic scales, key mineral assemblages and facies of metamorphism, temperature conditions of metamorphism, ages of metamorphism events and the massif rocks, genetic-geodynamic types of magmatic rocks. Explanatory note, attached to the map includes the large specter of scientific information. It contains characterization of the geological setting, composition and petrogenetic and geodynamic models of the massif formation. To create a geological map of the Loki crystalline massif, appropriate methodologies were applied: a sampling of rocks, GIS technology-based mapping of geological units, microscopic description of the material, composition analysis of rocks, microprobe analysis of minerals and a new interpretation of obtained data. To prepare a digital version of the map the appropriated activities were held including the creation of a common database. Finally, the design was created that includes the elaboration of legend and the final visualization of the map. The results of the study presented in the explanatory note are given below. The autochthonous gneissose quartz diorites of normal alkalinity and sub-alkaline gabbro-diorites included in them belong to different phases of magmatism. They represent “igneous” granites corresponding to mixed mantle-crustal type granites. Four tectonic plates of the allochthonous metamorphic complex–Lower Gorastskali, Sapharlo–Lok-Jandari, Moshevani, and Lower Gorastskali differ from each other by structure and degree of metamorphism. The initial rocks of these plates are formed in different geodynamic conditions and during the Early Bretonian orogeny while overthrusting due to tectonic compression they form a thick tectonic sheet. The Lower Gorastskali overthrust sheet is a fragment of ophiolitic association corresponding to the Paleotethys oceanic crust. The protolith of the ophiolitic complex basites corresponds to the tholeiitic series of basalts. The Sapharlo–Lok-Jandari overthrust sheet is metapelites, metamorphosed in conditions of greenschist facies of regional metamorphism. The regional metamorphism of Moshevani overthrust sheet crystalline schists quartzites corresponds to a range from greenschist to hornfels facies. The “mélange” is built of rock fragments and blocks of above-mentioned overthrust sheets. Sub-alkaline and normal alkaline post-metamorphic granites of the Loki crystalline massif belong to “igneous” and rarely to “sialic” and “anorogenic” types of granites.

Keywords: digital geological map, 1:50 000 scale, crystalline massif, the caucasus

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Authors: Jeremie Coullon, Robert J. Webber

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We introduce a Markov chain Monte Carlo (MCMC) sam-pler for infinite-dimensional inverse problems. Our sam-pler is based on the affine invariant ensemble sampler, which uses interacting walkers to adapt to the covariance structure of the target distribution. We extend this ensem-ble sampler for the first time to infinite-dimensional func-tion spaces, yielding a highly efficient gradient-free MCMC algorithm. Because our ensemble sampler does not require gradients or posterior covariance estimates, it is simple to implement and broadly applicable. In many Bayes-ian inverse problems, Markov chain Monte Carlo (MCMC) meth-ods are needed to approximate distributions on infinite-dimensional function spaces, for example, in groundwater flow, medical imaging, and traffic flow. Yet designing efficient MCMC methods for function spaces has proved challenging. Recent gradi-ent-based MCMC methods preconditioned MCMC methods, and SMC methods have improved the computational efficiency of functional random walk. However, these samplers require gradi-ents or posterior covariance estimates that may be challenging to obtain. Calculating gradients is difficult or impossible in many high-dimensional inverse problems involving a numerical integra-tor with a black-box code base. Additionally, accurately estimating posterior covariances can require a lengthy pilot run or adaptation period. These concerns raise the question: is there a functional sampler that outperforms functional random walk without requir-ing gradients or posterior covariance estimates? To address this question, we consider a gradient-free sampler that avoids explicit covariance estimation yet adapts naturally to the covariance struc-ture of the sampled distribution. This sampler works by consider-ing an ensemble of walkers and interpolating and extrapolating between walkers to make a proposal. This is called the affine in-variant ensemble sampler (AIES), which is easy to tune, easy to parallelize, and efficient at sampling spaces of moderate dimen-sionality (less than 20). The main contribution of this work is to propose a functional ensemble sampler (FES) that combines func-tional random walk and AIES. To apply this sampler, we first cal-culate the Karhunen–Loeve (KL) expansion for the Bayesian prior distribution, assumed to be Gaussian and trace-class. Then, we use AIES to sample the posterior distribution on the low-wavenumber KL components and use the functional random walk to sample the posterior distribution on the high-wavenumber KL components. Alternating between AIES and functional random walk updates, we obtain our functional ensemble sampler that is efficient and easy to use without requiring detailed knowledge of the target dis-tribution. In past work, several authors have proposed splitting the Bayesian posterior into low-wavenumber and high-wavenumber components and then applying enhanced sampling to the low-wavenumber components. Yet compared to these other samplers, FES is unique in its simplicity and broad applicability. FES does not require any derivatives, and the need for derivative-free sam-plers has previously been emphasized. FES also eliminates the requirement for posterior covariance estimates. Lastly, FES is more efficient than other gradient-free samplers in our tests. In two nu-merical examples, we apply FES to challenging inverse problems that involve estimating a functional parameter and one or more scalar parameters. We compare the performance of functional random walk, FES, and an alternative derivative-free sampler that explicitly estimates the posterior covariance matrix. We conclude that FES is the fastest available gradient-free sampler for these challenging and multimodal test problems.

Keywords: Bayesian inverse problems, Markov chain Monte Carlo, infinite-dimensional inverse problems, dimensionality reduction

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Authors: Ariesny Vera, Rodrigo Montecinos

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The rare-earth elements (REEs) or rare-earth metals (REMs), correspond to seventeen chemical elements composed by the fifteen lanthanoids, as well as scandium and yttrium. Lanthanoids corresponds to lanthanum and the f-block elements, from cerium to lutetium. Scandium and yttrium are considered rare-earth elements because they have ionic radii similar to the lighter f-block elements. These elements were called rare earths because they are simply more difficult to extract and separate individually than the most metals and, generally, they do not accumulate in minerals, they are rarely found in easily mined ores and are often unfavorably distributed in common ores/minerals. REEs show unique chemical and physical properties, in comparison to the other metals in the periodic table. Nowadays, these physicochemical properties are utilized in a wide range of synthetic, catalytic, electronic, medicinal, and military applications. Because of their applications, the global demand for rare earth metals is becoming progressively more important in the transition to a self-sustaining society and greener economy. However, due to the difficult separation between lanthanoid ions, the high cost and pollution of these processes, the scientists search the development of a method that combines selectivity and quantitative separation of lanthanoids from the leaching liquor, while being more economical and environmentally friendly processes. This motivation has favored the design and development of more efficient and environmentally friendly cation extractors with the incorporation of compounds as ionic liquids, membrane inclusion polymers (PIM) and supramolecular systems. Supramolecular chemistry focuses on the development of host-guest systems, in which a host molecule can recognize and bind a certain guest molecule or ion. Normally, the formation of a host-guest complex involves non-covalent interactions Additionally, host-guest interactions can be influenced among others effects by the structural nature of host and guests. The different macrocyclic hosts for lanthanoid species that have been studied are crown ethers, cyclodextrins, cucurbituryls, calixarenes and pillararenes.Among all the factors that can influence and affect lanthanoid (III) coordination, perhaps the most basic of them is the systematic control using macrocyclic substituents that promote a selective coordination. In this sense, macrocycles pillar[n]arenes (P[n]As) present a relatively easy functionalization and they have more π-rich cavity than other host molecules. This gives to P[n]As a negative electrostatic potential in the cavity which would be responsible for the selectivity of these compounds towards cations. Furthermore, the cavity size, the linker, and the functional groups of the polar headgroups could be modified in order to control the association of lanthanoid cations. In this sense, different P[n]As systems, specifically derivatives of the pentamer P[5]A functionalized with amide, amine, phosphate and sulfate derivatives, have been designed in terms of experimental synthesis and molecular dynamics, and the interaction between these P[5]As and some lanthanoid ions such as La³+, Eu³+ and Lu³+ has been studied by physicochemical characterization by 1H-NMR, ITC and fluorescence in the case of Eu³+ systems. The molecular dynamics study of these systems was developed in hexane as solvent, also taking into account the lanthanoid ions mentioned above, and the respective comparison studies between the different ions.

Keywords: lanthanoids, macrocycles, pillar[n]arenes, rare-earth metal extraction, supramolecular chemistry, supramolecular complexes.

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Authors: Ling Ai, Ziyu Zhao, Zeyu Zhou, Xiaochen Yang, Heng Zhai, Stuart Holmes

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Optimizing the catalyst layer structure is crucial for enhancing the performance of proton exchange membrane fuel cells (PEMFCs) with low Platinum (Pt) loading. Current works focused on the utilization, durability, and site activity of Pt particles on support, and performance enhancement has been achieved by loading Pt onto porous support with different morphology, such as graphene, carbon fiber, and carbon black. Some schemes have also incorporated cost considerations to achieve lower Pt loading. However, the design of the catalyst layer (CL) structure in the membrane electrode assembly (MEA) must consider the interactions between the layers. Addressing the crucial aspects of water management, low contact resistance, and the establishment of effective three-phase boundary for MEA, multi-walled carbon nanotubes (MWCNTs) are promising CL support due to their intrinsically high hydrophobicity, high axial electrical conductivity, and potential for ordered alignment. However, the drawbacks of MWCNTs, such as strong agglomeration, wall surface chemical inertness, and unopened ends, are unfavorable for Pt nanoparticle loading, which is detrimental to MEA processing and leads to inhomogeneous CL surfaces. This further deteriorates the utilization of Pt and increases the contact resistance. Robust chemical oxidation or nitrogen doping can introduce polar functional groups onto the surface of MWCNTs, facilitating the creation of open tube ends and inducing defects in tube walls. This improves dispersibility and load capacity but reduces length and conductivity. Consequently, a trade-off exists between maintaining the intrinsic properties and the degree of functionalization of MWCNTs. In this work, MWCNTs were modified based on the operational requirements of the MEA from the viewpoint of interlayer interactions, including the search for the optimal degree of oxidation, N-doping, and micro-arrangement. MWCNT were functionalized by oxidizing, N-doping, as well as micro-alignment to achieve lower contact resistance between CL and proton exchange membrane (PEM), better hydrophobicity, and enhanced performance. Furthermore, this work expects to construct a more continuously distributed three-phase boundary by aligning MWCNT to form a locally ordered structure, which is essential for the efficient utilization of Pt active sites. Different from other chemical oxidation schemes that used HNO3:H2SO4 (1:3) mixed acid to strongly oxidize MWCNT, this scheme adopted pure HNO3 to partially oxidize MWCNT at a lower reflux temperature (80 ℃) and a shorter treatment time (0 to 10 h) to preserve the morphology and intrinsic conductivity of MWCNT. The maximum power density of 979.81 mw cm-2 was achieved by Pt loading on 6h MWCNT oxidation time (Pt-MWCNT6h). This represented a 59.53% improvement over the commercial Pt/C catalyst of 614.17 (mw cm-2). In addition, due to the stronger electrical conductivity, the charge transfer resistance of Pt-MWCNT6h in the electrochemical impedance spectroscopy (EIS) test was 0.09 Ohm cm-2, which was 48.86% lower than that of Pt/C. This study will discuss the developed catalysts and their efficacy in a working fuel cell system. This research will validate the impact of low-functionalization modification of MWCNTs on the performance of PEMFC, which simplifies the preparation challenges of CL and contributing for the widespread commercial application of PEMFCs on a larger scale.

Keywords: carbon nanotubes, electrocatalyst, membrane electrode assembly, proton exchange membrane fuel cell

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Authors: J. van Soest, B. Bruneel, J. Smit, N. Williams, P. Swiegers

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Selenium (Se) is an essential trace mineral involved in reducing oxidative stress, enhancing immune status, improving reproduction, and regulating growth. During finishing period, selenium supplementation can be applied to improve meat quality. Dietary selenium can be provided in inorganic or organic forms. Specifically, L-selenomethionine (organic selenium) allows for selenium storage in animal protein which supports the animal during periods of high oxidative stress. The objective of this study was to investigate the effects of synthetically produced, single amino acid, L-selenomethionine (Excential Selenium 4000, Orffa Additives BV) on production parameters, health status, and meat quality of Bonsmara bull calves. 24 calves, 7 months of age, completed a 60-day initial growing period at a commercial feedlot, after which they were transported to research station Rumen-8 (Bethlehem, South-Africa). After a ten-day adaptation period, the bulls were allocated to a control (n=12) or treatment (n=12) group. Each group was divided over 3 pens based on weight. Both groups received Total Mixed Ration supplemented with 5.25 mg Se/head per day. The control group was supplemented with sodium selenite as Se source, whilst the treatment group was supplemented with L-selenomethionine (Excential Selenium 4000, Orffa Additives BV). Animals were limited to 10 kg feed intake per head per day to ensure similar Se intake. Treatment period lasted 1.5 months. A beta-adrenergic agonist was included in the feed for the last 30 days. During the treatment period, average daily gain, average daily feed intake, and feed conversion ratio were recorded. Blood parameters were measured at day 1, day 25, and before slaughter (day 47). After slaughter, carcass weight, dressing percentage, grading, and meat quality (pH, tenderness, colour, odour, purge, proximate analyses, acid detergent fibre, and neutral detergent fibre) were determined. No differences between groups were found in performance. A higher number of animals with cortisol levels below detection limit (27.6 nmol/l) was recorded for the treatment group. Other blood parameters showed no differences. No differences were found regarding carcass weight and dressing percentage. Important parameters of meat quality were significantly improved in the treatment group: instrumental tenderness at 14 days ageing was 2.8 and 3.4 for treatment and control respectively (P=0.010), and a 0.5% decrease in purge (of fresh samples) was shown, 1.5% and 2.0% for treatment group and control respectively (p=0.029). Besides, pH was shown to be numerically reduced in the treatment group. In summary, supplementation with L-selenomethionine as selenium source improved meat quality compared to sodium selenite. Lower instrumental tenderness (Warner Bratzler Shear Force, WBSF) was recorded for the treatment group. This indicates less tough meat and highest consumer satisfaction. Regarding purge, control was just below 2.0%, an important threshold for consumer acceptation. Treatment group scored 0.5% lower for purge than control, indicating higher consumer satisfaction. The lower pH in the treatment group could be an indication of higher glycogen reserves in muscle which could contribute to a reduced risk of Dark Firm Dry carcasses. More animals showed cortisol levels below detection limit in the treatment group, indicating lower levels of stress when animals receive L-selenomethionine.

Keywords: calves, meat quality, nutrition, selenium

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Authors: Hari Krishan Sharma, Sanjay Kumar Sharma, Sushil Kumar Swar

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Inadequate transverse reinforcement is considered as the main reason for the beam column joint shear failure observed during recent earthquakes. DSP matrix consists of cement and high content of micro-silica with low water to cement ratio while the aggregates are graded quartz sand. The use of reinforcing fibres leads not only to the increase of tensile/bending strength and specific fracture energy, but also to reduction of brittleness and, consequently, to production of non-explosive ruptures. Besides, fibre-reinforced materials are more homogeneous and less sensitive to small defects and flaws. Recent works on the freeze-thaw durability (also in the presence of de-icing salts) of fibre-reinforced DSP confirm the excellent behaviour in the expected long term service life.DSP materials, including fibre-reinforced DSP and CRC (Compact Reinforced Composites) are obtained by using high quantities of super plasticizers and high volumes of micro-silica. Steel fibres with high tensile yield strength of smaller diameter and short length in different fibre volume percentage and aspect ratio tilized to improve the performance by reducing the brittleness of matrix material. In the case of High Performance Densified Small Particle Concrete (HPDSPC), concrete is dense at the micro-structure level, tensile strain would be much higher than that of the conventional SFRC, SIFCON & SIMCON. Beam-column sub-assemblages used as moment resisting constructed using HPDSPC in the joint region with varying quantities of steel fibres, fibre aspect ratio and fibre orientation in the critical section. These HPDSPC in the joint region sub-assemblages tested under cyclic/earthquake loading. Besides loading measurements, frame displacements, diagonal joint strain and rebar strain adjacent to the joint will also be measured to investigate stress-strain behaviour, load deformation characteristics, joint shear strength, failure mechanism, ductility associated parameters, stiffness and energy dissipated parameters of the beam column sub-assemblages also evaluated. Finally a design procedure for the optimum design of HPDSPC corresponding to moment, shear forces and axial forces for the reinforced concrete beam-column joint sub-assemblage proposed. The fact that the implementation of material brittleness measure in the design of RC structures can improve structural reliability by providing uniform safety margins over a wide range of structural sizes and material compositions well recognized in the structural design and research. This lead to the development of high performance concrete for the optimized combination of various structural ratios in concrete for the optimized combination of various structural properties. The structural applications of HPDSPC, because of extremely high strength, will reduce dead load significantly as compared to normal weight concrete thereby offering substantial cost saving and by providing improved seismic response, longer spans, and thinner sections, less reinforcing steel and lower foundation cost. These cost effective parameters will make this material more versatile for use in various structural applications like beam-column joints in industries, airports, parking areas, docks, harbours, and also containers for hazardous material, safety boxes and mould & tools for polymer composites and metals.

Keywords: high performance densified small particle concrete (HPDSPC), steel fibre reinforced concrete (SFRC), slurry infiltrated concrete (SIFCON), Slurry infiltrated mat concrete (SIMCON)

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Authors: Sarah Niklas, Lynne Chester, Mark Diesendorf

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Geopolitical tensions, climate change and recent movements favouring a transformative shift in institutional power structures have influenced the economics of conventional energy supply for decades. This study takes a multi-dimensional approach to illustrate the potential of renewable energy (RE) technology to provide a pathway to a low-carbon economy driven by ecologically sustainable, independent and socially just energy. This comparative analysis identifies economic, political and social drivers that shaped the adoption of RE policy in two significantly different economies, Germany and Australia, with strong and weak commitments to RE respectively. Two complementary political-economy theories frame the document-based analysis. Régulation Theory, inspired by Marxist ideas and strongly influenced by contemporary economic problems, provides the background to explore the social relationships contributing the adoption of RE within the macro-economy. Varieties of Capitalism theory, a more recently developed micro-economic approach, examines the nature of state-firm relationships. Together these approaches provide a comprehensive lens of analysis. Germany’s energy policy transformed substantially over the second half of the last century. The development is characterised by the coordination of societal, environmental and industrial demands throughout the advancement of capitalist regimes. In the Fordist regime, mass production based on coal drove Germany’s astounding economic recovery during the post-war period. Economic depression and the instability of institutional arrangements necessitated the impulsive seeking of national security and energy independence. During the postwar Flexi-Fordist period, quality-based production, innovation and technology-based competition schemes, particularly with regard to political power structures in and across Europe, favoured the adoption of RE. Innovation, knowledge and education were institutionalized, leading to the legislation of environmental concerns. Lastly the establishment of government-industry-based coordinative programs supported the phase out of nuclear power and the increased adoption of RE during the last decade. Australia’s energy policy is shaped by the country’s richness in mineral resources. Energy policy largely served coal mining, historically and currently one of the most capital-intense industry. Assisted by the macro-economic dimensions of institutional arrangements, social and financial capital is orientated towards the export-led and strongly demand-oriented economy. Here energy policy serves the maintenance of capital accumulation in the mining sector and the emerging Asian economies. The adoption of supportive renewable energy policy would challenge the distinct role of the mining industry within the (neo)-liberal market economy. The state’s protective role of the mining sector has resulted in weak commitment to RE policy and investment uncertainty in the energy sector. Recent developments, driven by strong public support for RE, emphasize the sense of community in urban and rural areas and the emergence of a bottom-up approach to adopt renewables. Thus, political economy frameworks on both the macro-economic (Regulation Theory) and micro-economic (Varieties of Capitalism theory) scales can together explain the strong commitment to RE in Germany vis-à-vis the weak commitment in Australia.

Keywords: political economy, regulation theory, renewable energy, social relationships, energy transitions

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Authors: Agman Gupta, Rajashekar Badam, Noriyoshi Matsumi

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Introduction: Recently, silicon has been recognized as one of the potential alternatives as anode active material in Li-ion batteries (LIBs) to replace the conventionally used graphite anodes. Silicon is abundantly present in the nature, it can alloy with lithium metal, and has a higher theoretical capacity (~4200 mAhg-1) that is approximately 10 times higher than graphite. However, because of a large volume expansion (~400%) upon repeated de-/alloying, the pulverization of Si particles causes the exfoliation of electrode laminate leading to the loss of electrical contact and adversely affecting the formation of solid-electrolyte interface (SEI).1 Functional polymers as binders have emerged as a competitive strategy to mitigate these drawbacks and failure mechanism of silicon anodes.1 A variety of aqueous/non-aqueous polymer binders like sodium carboxy-methyl cellulose (CMC-Na), styrene butadiene rubber (SBR), poly(acrylic acid), and other variants like mussel inspired binders have been investigated to overcome these drawbacks.1 However, there are only a few reports that mention the attempt of addressing all the drawbacks associated with silicon anodes effectively using a single novel functional polymer system as a binder. In this regard, here, we report a novel highly robust n-type bisiminoacenaphthenequinone (BIAN)-paraphenylene-based crosslinked polymer as a binder for Si anodes in lithium-ion batteries (Fig. 1). On its application, crosslinked-BIAN binder was evaluated to provide mechanical robustness to the large volume expansion of Si particles, maintain electrical conductivity within the electrode laminate, and facilitate in the formation of a thin SEI by restricting the extent of electrolyte decomposition on the surface of anode. The fabricated anodic half-cells were evaluated electrochemically for their rate capability, cyclability, and discharge capacity. Experimental: The polymerized BIAN (P-BIAN) copolymer was synthesized as per the procedure reported by our group.2 The synthesis of crosslinked P-BIAN: a solution of P-BIAN copolymer (1.497 g, 10 mmol) in N-methylpyrrolidone (NMP) (150 ml) was set-up to stir under reflux in nitrogen atmosphere. To this, 1,6-dibromohexane (5 mmol, 0.77 ml) was added dropwise. The resultant reaction mixture was stirred and refluxed at 150 °C for 24 hours followed by refrigeration for 3 hours at 5 °C. The product was obtained by evaporating the NMP solvent under reduced pressure and drying under vacuum at 120 °C for 12 hours. The obtained product was a black colored sticky compound. It was characterized by 1H-NMR, XPS, and FT-IR techniques. Results and Discussion: The N 1s XPS spectrum of the crosslinked BIAN polymer showed two characteristic peaks corresponding to the sp2 hybridized nitrogen (-C=N-) at 399.6 eV of the diimine backbone in the BP and quaternary nitrogen at 400.7 eV corresponding to the crosslinking of BP via dibromohexane. The DFT evaluation of the crosslinked BIAN binder showed that it has a low lying lowest unoccupied molecular orbital (LUMO) that enables it to get doped in the reducing environment and influence the formation of a thin (SEI). Therefore, due to the mechanically robust crosslinked matrices as well as its influence on the formation of a thin SEI, the crosslinked BIAN binder stabilized the Si anode-based half-cell for over 1000 cycles with a reversible capacity of ~2500 mAhg-1 and ~99% capacity retention as shown in Fig. 2. The dynamic electrochemical impedance spectroscopy (DEIS) characterization of crosslinked BIAN-based anodic half-cell confirmed that the SEI formed was thin in comparison with the conventional binder-based anodes. Acknowledgement: We are thankful to the financial support provided by JST-Mirai Program, Grant Number: JP18077239

Keywords: self-healing binder, n-type binder, thin solid-electrolyte interphase (SEI), high-capacity silicon anodes, low-LUMO

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Authors: Charaia Vakhtang

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Global oil prices are seeing new bottoms every day. The prices have already collapsed beneath the psychological verge of 30 USD. This tendency would be fully acceptable for the Georgian consumers, but there is one detail: two our neighboring countries (one friendly and one hostile) largely depend on resources of these hydrocarbons. Namely, the ratio of Azerbaijan in Georgia’s total FDI inflows in 2014 marked 20%. The ratio reached 40% in the January to September 2015. Azerbaijan is Georgia’s leading exports market. Namely, in 2014 Georgia’s exports to Azerbaijan constituted 544 million USD, i.e. 19% in Georgia’s total experts. In the January to November period of 2015, the ratio exceeded 11%. Moreover, Azerbaijan is Georgia’s strategic partner country as part of many regional projects that are designated for long-term perspectives. For example, the Baku-Tbilisi-Karsi railroad, the Black Sea terminal, preferential gas tariffs for Georgia and so on. The Russian economic contribution to the Georgian economy is also considerable, despite the losses the Russian hostile policy has inflicted to our country. Namely, Georgian emigrants are mainly employed in the Russian Federation and this category of Georgian citizens transfers considerable funds to Georgia every year. These transfers account for about 1 billion USD and consequently, these funds previously equalized to total FDI inflows. Moreover, despite the difficulties in the Russian market, Russia still remains a leader in terms of money transfers to Georgia. According to the last reports, money transfers from Russia to Georgia slipped by 276 million USD in 2015 compared to 2014 (-39%). At the same time, the total money transfers to Georgia in 2015 marked 1.08 billion USD, down 25% from 1.44 billion USD in 2014. This signifies the contraction in money transfers is by ¾ dependent on the Russian factor (in this case, contraction in oil prices and the Russian Ruble devaluation directly make negative impact on money transfers to Georgia). As to other countries, it is interesting that money transfers have also slipped from Italy (to 109 million USD from 121 million USD). Nevertheless, the country’s ratio in total money transfers to Georgia has increased to 10% from 8%. Money transfers to Georgia have increased by 22% (+18 million USD) from the USA. Money transfers have halved from Greece to 117 million USD from 205 million USD. As to Turkey, money transfers to Georgia from Turkey have increased by 1% to 69 million USD. Moreover, the problems with the national currencies of Russia and Azerbaijan, along with the above-mentioned developments, outline unfavorable perspectives for the Georgian economy. The depreciation of the national currencies of Azerbaijan and Russia is expected to bring unfavorable results for the Georgian economy. Even more so, the statement released by the Russian Finance Ministry on expected default is in direct relation to the welfare of the whole region and these tendencies will make direct and indirect negative impacts on Georgia’s economic indicators. Amid the economic slowdown in Armenia, Turkey and Ukraine, Georgia should try to enhance economic ties with comparatively stronger and flexible economies such as EU and USA. In other case, the Georgian economy will enter serious turbulent zone. We should make maximum benefit from the EU association agreement. It should be noted that the Russian economy slowdown that causes both regretful and happy moods in Georgia, will make negative impact on the Georgian economy. The same forecasts are made in relation to Azerbaijan. However, Georgia has many partner countries. Enhancement and development of the economic relations with these countries may maximally alleviate negative impacts from the declining economies. First of all, the EU association agreement should be mentioned as a main source for Georgia’s economic stabilization. It is the Georgian government‘s responsibility to successfully fulfill the EU association agreement requirements. In any case the imports must be replaced by domestic products and the exports should be stimulated through government support programs. The Authorities should ensure drawing more foreign investments and money resources, accumulating more tourism revenues and reducing external debts, budget expenditures should be balanced and the National Bank should carry out strict monetary policy. Moreover, the Government should develop a long-term state economic policy and carry out this policy at various Ministries. It is also of crucial importance to carry out constitutive policy and promote perspective directions on the domestic level.

Keywords: oil prices, economic growth, foreign direct investments, international trade

Procedia PDF Downloads 249