Search results for: laser emission
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 2271

Search results for: laser emission

81 The Budget Impact of the DISCERN™ Diagnostic Test for Alzheimer’s Disease in the United States

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

Abstract:

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

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

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80 Xen45 Gel Implant in Open Angle Glaucoma: Efficacy, Safety and Predictors of Outcome

Authors: Fossarello Maurizio, Mattana Giorgio, Tatti Filippo.

Abstract:

The most widely performed surgical procedure in Open-Angle Glaucoma (OAG) is trabeculectomy. Although this filtering procedure is extremely effective, surgical failure and postoperative complications are reported. Due to the its invasive nature and possible complications, trabeculectomy is usually reserved, in practice, for patients who are refractory to medical and laser therapy. Recently, a number of micro-invasive surgical techniques (MIGS: Micro-Invasive Glaucoma Surgery), have been introduced in clinical practice. They meet the criteria of micro-incisional approach, minimal tissue damage, short surgical time, reliable IOP reduction, extremely high safety profile and rapid post-operative recovery. Xen45 Gel Implant (Allergan, Dublin, Ireland) is one of the MIGS alternatives, and consists in a porcine gelatin tube designed to create an aqueous flow from the anterior chamber to the subconjunctival space, bypassing the resistance of the trabecular meshwork. In this study we report the results of this technique as a favorable option in the treatment of OAG for its benefits in term of efficacy and safety, either alone or in combination with cataract surgery. This is a retrospective, single-center study conducted in consecutive OAG patients, who underwent Xen45 Gel Stent implantation alone or in combination with phacoemulsification, from October 2018 to June 2019. The primary endpoint of the study was to evaluate the reduction of both IOP and number of antiglaucoma medications at 12 months. The secondary endpoint was to correlate filtering bleb morphology evaluated by means of anterior segment OCT with efficacy in IOP lowering and eventual further procedures requirement. Data were recorded on Microsoft Excel and study analysis was performed using Microsoft Excel and SPSS (IBM). Mean values with standard deviations were calculated for IOPs and number of antiglaucoma medications at all points. Kolmogorov-Smirnov test showed that IOP followed a normal distribution at all time, therefore the paired Student’s T test was used to compare baseline and postoperative mean IOP. Correlation between postoperative Day 1 IOP and Month 12 IOP was evaluated using Pearson coefficient. Thirty-six eyes of 36 patients were evaluated. As compared to baseline, mean IOP and the mean number of antiglaucoma medications significantly decreased from 27,33 ± 7,67 mmHg to 16,3 ± 2,89 mmHg (38,8% reduction) and from 2,64 ± 1,39 to 0,42 ± 0,8 (84% reduction), respectively, at 12 months after surgery (both p < 0,001). According to bleb morphology, eyes were divided in uniform group (n=8, 22,2%), subconjunctival separation group (n=5, 13,9%), microcystic multiform group (n=9, 25%) and multiple internal layer group (n=14, 38,9%). Comparing to baseline, there was no significative difference in IOP between the 4 groups at month 12 follow-up visit. Adverse events included bleb function decrease (n=14, 38,9%), hypotony (n=8, 22,2%) and choroidal detachment (n=2, 5,6%). All eyes presenting bleb flattening underwent needling and MMC injection. The higher percentage of patients that required secondary needling was in the uniform group (75%), with a significant difference between the groups (p=0,03). Xen45 gel stent, either alone or in combination with phacoemulsification, provided a significant lowering in both IOP and medical antiglaucoma treatment and an elevated safety profile.

Keywords: anterior segment OCT, bleb morphology, micro-invasive glaucoma surgery, open angle glaucoma, Xen45 gel implant

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79 Hydrogen Production from Auto-Thermal Reforming of Ethanol Catalyzed by Tri-Metallic Catalyst

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

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

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

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78 Reconstruction of Signal in Plastic Scintillator of PET Using Tikhonov Regularization

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

Abstract:

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

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

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77 Biostabilisation of Sediments for the Protection of Marine Infrastructure from Scour

Authors: Rob Schindler

Abstract:

Industry-standard methods of mitigating erosion of seabed sediments rely on ‘hard engineering’ approaches which have numerous environmental shortcomings: (1) direct loss of habitat by smothering of benthic species, (2) disruption of sediment transport processes, damaging geomorphic and ecosystem functionality (3) generation of secondary erosion problems, (4) introduction of material that may propagate non-local species, and (5) provision of pathways for the spread of invasive species. Recent studies have also revealed the importance of biological cohesion, the result of naturally occurring extra-cellular polymeric substances (EPS), in stabilizing natural sediments. Mimicking the strong bonding kinetics through the deliberate addition of EPS to sediments – henceforth termed ‘biostabilisation’ - offers a means in which to mitigate against erosion induced by structures or episodic increases in hydrodynamic forcing (e.g. storms and floods) whilst avoiding, or reducing, hard engineering. Here we present unique experiments that systematically examine how biostabilisation reduces scour around a monopile in a current, a first step to realizing the potential of this new method of scouring reduction for a wide range of engineering purposes in aquatic substrates. Experiments were performed in Plymouth University’s recirculating sediment flume which includes a recessed scour pit. The model monopile was 0.048 m in diameter, D. Assuming a prototype monopile diameter of 2.0 m yields a geometric ratio of 41.67. When applied to a 10 m prototype water depth this yields a model depth, d, of 0.24 m. The sediment pit containing the monopile was filled with different biostabilised substrata prepared using a mixture of fine sand (D50 = 230 μm) and EPS (Xanthan gum). Nine sand-EPS mixtures were examined spanning EPS contents of 0.0% < b0 < 0.50%. Scour development was measured using a laser point gauge along a 530 mm centreline at 10 mm increments at regular periods over 5 h. Maximum scour depth and excavated area were determined at different time steps and plotted against time to yield equilibrium values. After 5 hours the current was stopped and a detailed scan of the final scour morphology was taken. Results show that increasing EPS content causes a progressive reduction in the equilibrium depth and lateral extent of scour, and hence excavated material. Very small amounts equating to natural communities (< 0.1% by mass) reduce scour rate, depth and extent of scour around monopiles. Furthermore, the strong linear relationships between EPS content, equilibrium scour depth, excavation area and timescales of scouring offer a simple index on which to modify existing scour prediction methods. We conclude that the biostabilisation of sediments with EPS may offer a simple, cost-effective and ecologically sensitive means of reducing scour in a range of contexts including OWFs, bridge piers, pipeline installation, and void filling in rock armour. Biostabilisation may also reduce economic costs through (1) Use of existing site sediments, or waste dredged sediments (2) Reduced fabrication of materials, (3) Lower transport costs, (4) Less dependence on specialist vessels and precise sub-sea assembly. Further, its potential environmental credentials may allow sensitive use of the seabed in marine protection zones across the globe.

Keywords: biostabilisation, EPS, marine, scour

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76 Environmental Impact of Pallets in the Supply Chain: Including Logistics and Material Durability in a Life Cycle Assessment Approach

Authors: Joana Almeida, Kendall Reid, Jonas Bengtsson

Abstract:

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

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

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

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

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

Keywords: casting, cast iron, microstructure, heat treating

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74 A Study of the Carbon Footprint from a Liquid Silicone Rubber Compounding Facility in Malaysia

Authors: Q. R. Cheah, Y. F. Tan

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In modern times, the push for a low carbon footprint entails achieving carbon neutrality as a goal for future generations. One possible step towards carbon footprint reduction is the use of more durable materials with longer lifespans, for example, silicone data cableswhich show at least double the lifespan of similar plastic products. By having greater durability and longer lifespans, silicone data cables can reduce the amount of trash produced as compared to plastics. Furthermore, silicone products don’t produce micro contamination harmful to the ocean. Every year the electronics industry produces an estimated 5 billion data cables for USB type C and lightning data cables for tablets and mobile phone devices. Material usage for outer jacketing is 6 to 12 grams per meter. Tests show that the product lifespan of a silicone data cable over plastic can be doubled due to greater durability. This can save at least 40,000 tonnes of material a year just on the outer jacketing of the data cable. The facility in this study specialises in compounding of liquid silicone rubber (LSR) material for the extrusion process in jacketing for the silicone data cable. This study analyses the carbon emissions from the facility, which is presently capable of producing more than 1,000 tonnes of LSR annually. This study uses guidelines from the World Business Council for Sustainable Development (WBCSD) and World Resources Institute (WRI) to define the boundaries of the scope. The scope of emissions is defined as 1. Emissions from operations owned or controlled by the reporting company, 2. Emissions from the generation of purchased or acquired energy such as electricity, steam, heating, or cooling consumed by the reporting company, and 3. All other indirect emissions occurring in the value chain of the reporting company, including both upstream and downstream emissions. As the study is limited to the compounding facility, the system boundaries definition according to GHG protocol is cradle-to-gate instead of cradle-to-grave exercises. Malaysia’s present electricity generation scenario was also used, where natural gas and coal constitute the bulk of emissions. Calculations show the LSR produced for the silicone data cable with high fire retardant capability has scope 1 emissions of 0.82kg CO2/kg, scope 2 emissions of 0.87kg CO2/kg, and scope 3 emissions of 2.76kg CO2/kg, with a total product carbon footprint of 4.45kg CO2/kg. This total product carbon footprint (Cradle-to-gate) is comparable to the industry and to plastic materials per tonne of material. Although per tonne emission is comparable to plastic material, due to greater durability and longer lifespan, there can be significantly reduced use of LSR material. Suggestions to reduce the calculated product carbon footprint in the scope of emissions involve 1. Incorporating the recycling of factory silicone waste into operations, 2. Using green renewable energy for external electricity sources and 3. Sourcing eco-friendly raw materials with low GHG emissions.

Keywords: carbon footprint, liquid silicone rubber, silicone data cable, Malaysia facility

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73 Influence of a High-Resolution Land Cover Classification on Air Quality Modelling

Authors: C. Silveira, A. Ascenso, J. Ferreira, A. I. Miranda, P. Tuccella, G. Curci

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Poor air quality is one of the main environmental causes of premature deaths worldwide, and mainly in cities, where the majority of the population lives. It is a consequence of successive land cover (LC) and use changes, as a result of the intensification of human activities. Knowing these landscape modifications in a comprehensive spatiotemporal dimension is, therefore, essential for understanding variations in air pollutant concentrations. In this sense, the use of air quality models is very useful to simulate the physical and chemical processes that affect the dispersion and reaction of chemical species into the atmosphere. However, the modelling performance should always be evaluated since the resolution of the input datasets largely dictates the reliability of the air quality outcomes. Among these data, the updated LC is an important parameter to be considered in atmospheric models, since it takes into account the Earth’s surface changes due to natural and anthropic actions, and regulates the exchanges of fluxes (emissions, heat, moisture, etc.) between the soil and the air. This work aims to evaluate the performance of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), when different LC classifications are used as an input. The influence of two LC classifications was tested: i) the 24-classes USGS (United States Geological Survey) LC database included by default in the model, and the ii) CLC (Corine Land Cover) and specific high-resolution LC data for Portugal, reclassified according to the new USGS nomenclature (33-classes). Two distinct WRF-Chem simulations were carried out to assess the influence of the LC on air quality over Europe and Portugal, as a case study, for the year 2015, using the nesting technique over three simulation domains (25 km2, 5 km2 and 1 km2 horizontal resolution). Based on the 33-classes LC approach, particular emphasis was attributed to Portugal, given the detail and higher LC spatial resolution (100 m x 100 m) than the CLC data (5000 m x 5000 m). As regards to the air quality, only the LC impacts on tropospheric ozone concentrations were evaluated, because ozone pollution episodes typically occur in Portugal, in particular during the spring/summer, and there are few research works relating to this pollutant with LC changes. The WRF-Chem results were validated by season and station typology using background measurements from the Portuguese air quality monitoring network. As expected, a better model performance was achieved in rural stations: moderate correlation (0.4 – 0.7), BIAS (10 – 21µg.m-3) and RMSE (20 – 30 µg.m-3), and where higher average ozone concentrations were estimated. Comparing both simulations, small differences grounded on the Leaf Area Index and air temperature values were found, although the high-resolution LC approach shows a slight enhancement in the model evaluation. This highlights the role of the LC on the exchange of atmospheric fluxes, and stresses the need to consider a high-resolution LC characterization combined with other detailed model inputs, such as the emission inventory, to improve air quality assessment.

Keywords: land use, spatial resolution, WRF-Chem, air quality assessment

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72 Fabrication of High Energy Hybrid Capacitors from Biomass Waste-Derived Activated Carbon

Authors: Makhan Maharjan, Mani Ulaganathan, Vanchiappan Aravindan, Srinivasan Madhavi, Jing-Yuan Wang, Tuti Mariana Lim

Abstract:

There is great interest to exploit sustainable, low-cost, renewable resources as carbon precursors for energy storage applications. Research on development of energy storage devices has been growing rapidly due to mismatch in power supply and demand from renewable energy sources This paper reported the synthesis of porous activated carbon from biomass waste and evaluated its performance in supercapicators. In this work, we employed orange peel (waste material) as the starting material and synthesized activated carbon by pyrolysis of KOH impregnated orange peel char at 800 °C in argon atmosphere. The resultant orange peel-derived activated carbon (OP-AC) exhibited a high BET surface area of 1,901 m2 g-1, which is the highest surface area so far reported for the orange peel. The pore size distribution (PSD) curve exhibits the pores centered at 11.26 Å pore width, suggesting dominant microporosity. The OP-AC was studied as positive electrode in combination with different negative electrode materials, such as pre-lithiated graphite (LiC6) and Li4Ti5O12 for making different hybrid capacitors. The lithium ion capacitor (LIC) fabricated using OP-AC with pre-lithiated graphite delivered a high energy density of ~106 Wh kg–1. The energy density for OP-AC||Li4Ti5O12 capacitor was ~35 Wh kg–1. For comparison purpose, configuration of OP-AC||OP-AC capacitors were studied in both aqueous (1M H2SO4) and organic (1M LiPF6 in EC-DMC) electrolytes, which delivered the energy density of 6.6 Wh kg-1 and 16.3 Wh kg-1, respectively. The cycling retentions obtained at current density of 1 A g–1 were ~85.8, ~87.0 ~82.2 and ~58.8% after 2500 cycles for OP-AC||OP-AC (aqueous), OP-AC||OP-AC (organic), OP-AC||Li4Ti5O12 and OP-AC||LiC6 configurations, respectively. In addition, characterization studies were performed by elemental and proximate composition, thermogravimetry, field emission-scanning electron microscopy, Raman spectra, X-ray diffraction (XRD) pattern, Fourier transform-infrared, X-ray photoelectron spectroscopy (XPS) and N2 sorption isotherms. The morphological features from FE-SEM exhibited well-developed porous structures. Two typical broad peaks observed in the XRD framework of the synthesized carbon implies amorphous graphitic structure. The ratio of 0.86 for ID/IG in Raman spectra infers high degree of graphitization in the sample. The band spectra of C 1s in XPS display the well resolved peaks related to carbon atoms in various chemical environments; for instances, the characteristics binding energies appeared at ~283.83, ~284.83, ~286.13, ~288.56, and ~290.70 eV which correspond to sp2 -graphitic C, sp3 -graphitic C, C-O, C=O and π-π*, respectively. Characterization studies revealed the synthesized carbon to be promising electrode material towards the application for energy storage devices. The findings opened up the possibility of developing high energy LICs from abundant, low-cost, renewable biomass waste.

Keywords: lithium-ion capacitors, orange peel, pre-lithiated graphite, supercapacitors

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71 Electronic Raman Scattering Calibration for Quantitative Surface-Enhanced Raman Spectroscopy and Improved Biostatistical Analysis

Authors: Wonil Nam, Xiang Ren, Inyoung Kim, Masoud Agah, Wei Zhou

Abstract:

Despite its ultrasensitive detection capability, surface-enhanced Raman spectroscopy (SERS) faces challenges as a quantitative biochemical analysis tool due to the significant dependence of local field intensity in hotspots on nanoscale geometric variations of plasmonic nanostructures. Therefore, despite enormous progress in plasmonic nanoengineering of high-performance SERS devices, it is still challenging to quantitatively correlate the measured SERS signals with the actual molecule concentrations at hotspots. A significant effort has been devoted to developing SERS calibration methods by introducing internal standards. It has been achieved by placing Raman tags at plasmonic hotspots. Raman tags undergo similar SERS enhancement at the same hotspots, and ratiometric SERS signals for analytes of interest can be generated with reduced dependence on geometrical variations. However, using Raman tags still faces challenges for real-world applications, including spatial competition between the analyte and tags in hotspots, spectral interference, laser-induced degradation/desorption due to plasmon-enhanced photochemical/photothermal effects. We show that electronic Raman scattering (ERS) signals from metallic nanostructures at hotspots can serve as the internal calibration standard to enable quantitative SERS analysis and improve biostatistical analysis. We perform SERS with Au-SiO₂ multilayered metal-insulator-metal nano laminated plasmonic nanostructures. Since the ERS signal is proportional to the volume density of electron-hole occupation in hotspots, the ERS signals exponentially increase when the wavenumber is approaching the zero value. By a long-pass filter, generally used in backscattered SERS configurations, to chop the ERS background continuum, we can observe an ERS pseudo-peak, IERS. Both ERS and SERS processes experience the |E|⁴ local enhancements during the excitation and inelastic scattering transitions. We calibrated IMRS of 10 μM Rhodamine 6G in solution by IERS. The results show that ERS calibration generates a new analytical value, ISERS/IERS, insensitive to variations from different hotspots and thus can quantitatively reflect the molecular concentration information. Given the calibration capability of ERS signals, we performed label-free SERS analysis of living biological systems using four different breast normal and cancer cell lines cultured on nano-laminated SERS devices. 2D Raman mapping over 100 μm × 100 μm, containing several cells, was conducted. The SERS spectra were subsequently analyzed by multivariate analysis using partial least square discriminant analysis. Remarkably, after ERS calibration, MCF-10A and MCF-7 cells are further separated while the two triple-negative breast cancer cells (MDA-MB-231 and HCC-1806) are more overlapped, in good agreement with the well-known cancer categorization regarding the degree of malignancy. To assess the strength of ERS calibration, we further carried out a drug efficacy study using MDA-MB-231 and different concentrations of anti-cancer drug paclitaxel (PTX). After ERS calibration, we can more clearly segregate the control/low-dosage groups (0 and 1.5 nM), the middle-dosage group (5 nM), and the group treated with half-maximal inhibitory concentration (IC50, 15 nM). Therefore, we envision that ERS calibrated SERS can find crucial opportunities in label-free molecular profiling of complicated biological systems.

Keywords: cancer cell drug efficacy, plasmonics, surface-enhanced Raman spectroscopy (SERS), SERS calibration

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70 A Multipurpose Inertial Electrostatic Magnetic Confinement Fusion for Medical Isotopes Production

Authors: Yasser R. Shaban

Abstract:

A practical multipurpose device for medical isotopes production is most wanted for clinical centers and researches. Unfortunately, the major supply of these radioisotopes currently comes from aging sources, and there is a great deal of uneasiness in the domestic market. There are also many cases where the cost of certain radioisotopes is too high for their introduction on a commercial scale even though the isotopes might have great benefits for society. The medical isotopes such as radiotracers PET (Positron Emission Tomography), Technetium-99 m, and Iodine-131, Lutetium-177 by is feasible to be generated by a single unit named IEMC (Inertial Electrostatic Magnetic Confinement). The IEMC fusion vessel is the upgrading unit of the Inertial Electrostatic Confinement IEC fusion vessel. Comprehensive experimental works on IEC were carried earlier with promising results. The principle of inertial electrostatic magnetic confinement IEMC fusion is based on forcing the binary fuel ions to interact in the opposite directions in ions cyclotrons orbits with different kinetic energies in order to have equal compression (forces) and with different ion cyclotron frequency ω in order to increase the rate of intersection. The IEMC features greater fusion volume than IEC by several orders of magnitude. The particles rate from the IEMC approach are projected to be 8.5 x 10¹¹ (p/s), ~ 0.2 microampere proton, for D/He-3 fusion reaction and 4.2 x 10¹² (n/s) for D/T fusion reaction. The projected values of particles yield (neutrons and protons) are suitable for medical isotope productions on-site by a single unit without any change in the fusion vessel but only the fuel gas. The PET radiotracers are usually produced on-site by medical ion accelerator whereas Technetium-99m (Tc-99m) is usually produced off-site from the irradiation facilities of nuclear power plants. Typically, hospitals receive molybdenum-99 isotope container; the isotope decays to Tc-99mwith half-life time 2.75 days. Even though the projected current from IEMC is lesser than the proton current from the medical ion accelerator but still the IEMC vessel is simpler, and reduced in components and power consumption which add a new value of populating the PET radiotracers in most clinical centers. On the other hand, the projected neutrons flux from the IEMC is lesser than the thermal neutron flux at the irradiation facilities of nuclear power plants, but in the IEMC case the productions of Technetium-99m is suggested to be at the resonance region of which the resonance integral cross section is two orders of magnitude higher than the thermal flux. Thus it can be said the net activity from both is evened. Besides, the particle accelerator cannot be considered a multipurpose particles production unless a significant change is made to the accelerator to change from neutrons mode to protons mode or vice versa. In conclusion, the projected fusion yield from IEMC is a straightforward since slightly change in the primer IEC and ion source is required.

Keywords: electrostatic versus magnetic confinement fusion vessel, ion source, medical isotopes productions, neutron activation

Procedia PDF Downloads 343
69 Ammonia Cracking: Catalysts and Process Configurations for Enhanced Performance

Authors: Frea Van Steenweghen, Lander Hollevoet, Johan A. Martens

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Compared to other hydrogen (H₂) carriers, ammonia (NH₃) is one of the most promising carriers as it contains 17.6 wt% hydrogen. It is easily liquefied at ≈ 9–10 bar pressure at ambient temperature. More importantly, NH₃ is a carbon-free hydrogen carrier with no CO₂ emission at final decomposition. Ammonia has a well-defined regulatory framework and a good track record regarding safety concerns. Furthermore, the industry already has an existing transport infrastructure consisting of pipelines, tank trucks and shipping technology, as ammonia has been manufactured and distributed around the world for over a century. While NH₃ synthesis and transportation technological solutions are at hand, a missing link in the hydrogen delivery scheme from ammonia is an energy-lean and efficient technology for cracking ammonia into H₂ and N₂. The most explored option for ammonia decomposition is thermo-catalytic cracking which is, by itself, the most energy-efficient approach compared to other technologies, such as plasma and electrolysis, as it is the most energy-lean and robust option. The decomposition reaction is favoured only at high temperatures (> 300°C) and low pressures (1 bar) as the thermocatalytic ammonia cracking process is faced with thermodynamic limitations. At 350°C, the thermodynamic equilibrium at 1 bar pressure limits the conversion to 99%. Gaining additional conversion up to e.g. 99.9% necessitates heating to ca. 530°C. However, reaching thermodynamic equilibrium is infeasible as a sufficient driving force is needed, requiring even higher temperatures. Limiting the conversion below the equilibrium composition is a more economical option. Thermocatalytic ammonia cracking is documented in scientific literature. Among the investigated metal catalysts (Ru, Co, Ni, Fe, …), ruthenium is known to be most active for ammonia decomposition with an onset of cracking activity around 350°C. For establishing > 99% conversion reaction, temperatures close to 600°C are required. Such high temperatures are likely to reduce the round-trip efficiency but also the catalyst lifetime because of the sintering of the supported metal phase. In this research, the first focus was on catalyst bed design, avoiding diffusion limitation. Experiments in our packed bed tubular reactor set-up showed that extragranular diffusion limitations occur at low concentrations of NH₃ when reaching high conversion, a phenomenon often overlooked in experimental work. A second focus was thermocatalyst development for ammonia cracking, avoiding the use of noble metals. To this aim, candidate metals and mixtures were deposited on a range of supports. Sintering resistance at high temperatures and the basicity of the support were found to be crucial catalyst properties. The catalytic activity was promoted by adding alkaline and alkaline earth metals. A third focus was studying the optimum process configuration by process simulations. A trade-off between conversion and favorable operational conditions (i.e. low pressure and high temperature) may lead to different process configurations, each with its own pros and cons. For example, high-pressure cracking would eliminate the need for post-compression but is detrimental for the thermodynamic equilibrium, leading to an optimum in cracking pressure in terms of energy cost.

Keywords: ammonia cracking, catalyst research, kinetics, process simulation, thermodynamic equilibrium

Procedia PDF Downloads 68
68 CO2 Utilization by Reverse Water-Shift and Fischer-Tropsch Synthesis for Production of Heavier Fraction Hydrocarbons in a Container-Sized Mobile Unit

Authors: Francisco Vidal Vázquez, Pekka Simell, Christian Frilund, Matti Reinikainen, Ilkka Hiltunen, Tim Böltken, Benjamin Andris, Paolo Piermartini

Abstract:

Carbon capture and utilization (CCU) are one of the key topics in mitigation of CO2 emissions. There are many different technologies that are applied for the production of diverse chemicals from CO2 such as synthetic natural gas, Fischer-Tropsch products, methanol and polymers. Power-to-Gas and Power-to-Liquids concepts arise as a synergetic solution for storing energy and producing value added products from the intermittent renewable energy sources and CCU. VTT is a research and technology development company having energy in transition as one of the key focus areas. VTT has extensive experience in piloting and upscaling of new energy and chemical processes. Recently, VTT has developed and commissioned a Mobile Synthesis Unit (MOBSU) in close collaboration with INERATEC, a spin-off company of Karlsruhe Institute of Technology (KIT, Germany). The MOBSU is a multipurpose synthesis unit for CO2 upgrading to energy carriers and chemicals, which can be transported on-site where CO2 emission and renewable energy are available. The MOBSU is initially used for production of fuel compounds and chemical intermediates by combination of two consecutive processes: reverse Water-Gas Shift (rWGS) and Fischer-Tropsch synthesis (FT). First, CO2 is converted to CO by high-pressure rWGS and then, the CO and H2 rich effluent is used as feed for FT using an intensified reactor technology developed and designed by INERATEC. Chemical equilibrium of rWGS reaction is not affected by pressure. Nevertheless, compression would be required in between rWGS and FT in the case when rWGS is operated at atmospheric pressure. This would also require cooling of rWGS effluent, water removal and reheating. For that reason, rWGS is operated using precious metal catalyst in the MOBSU at similar pressure as FT to simplify the process. However, operating rWGS at high pressures has also some disadvantages such as methane and carbon formation, and more demanding specifications for materials. The main parts of FT module are an intensified reactor, a hot trap to condense the FT wax products, and a cold trap to condense the FT liquid products. The FT synthesis is performed using cobalt catalyst in a novel compact reactor technology with integrated highly-efficient water evaporation cooling cycle. The MOBSU started operation in November 2016. First, the FT module is tested using as feedstock H2 and CO. Subsequently, rWGS and FT modules are operated together using CO2 and H2 as feedstock of ca. 5 Nm3/hr total flowrate. On spring 2017, The MOBSU unit will be integrated together with a direct air capture (DAC) of CO2 unit, and a PEM electrolyser unit at Lappeenranta University of Technology (LUT) premises for demonstration of the SoletAir concept. This would be the first time when synthetic fuels are produced by combination of DAC unit and electrolyser unit which uses solar power for H2 production.

Keywords: CO2 utilization, demonstration, Fischer-Tropsch synthesis, intensified reactors, reverse water-gas shift

Procedia PDF Downloads 291
67 LES Simulation of a Thermal Plasma Jet with Modeled Anode Arc Attachment Effects

Authors: N. Agon, T. Kavka, J. Vierendeels, M. Hrabovský, G. Van Oost

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A plasma jet model was developed with a rigorous method for calculating the thermophysical properties of the gas mixture without mixing rules. A simplified model approach to account for the anode effects was incorporated in this model to allow the valorization of the simulations with experimental results. The radial heat transfer was under-predicted by the model because of the limitations of the radiation model, but the calculated evolution of centerline temperature, velocity and gas composition downstream of the torch exit corresponded well with the measured values. The CFD modeling of thermal plasmas is either focused on development of the plasma arc or the flow of the plasma jet outside of the plasma torch. In the former case, the Maxwell equations are coupled with the Navier-Stokes equations to account for electromagnetic effects which control the movements of the anode arc attachment. In plasma jet simulations, however, the computational domain starts from the exit nozzle of the plasma torch and the influence of the arc attachment fluctuations on the plasma jet flow field is not included in the calculations. In that case, the thermal plasma flow is described by temperature, velocity and concentration profiles at the torch exit nozzle and no electromagnetic effects are taken into account. This simplified approach is widely used in literature and generally acceptable for plasma torches with a circular anode inside the torch chamber. The unique DC hybrid water/gas-stabilized plasma torch developed at the Institute of Plasma Physics of the Czech Academy of Sciences on the other hand, consists of a rotating anode disk, located outside of the torch chamber. Neglecting the effects of the anode arc attachment downstream of the torch exit nozzle leads to erroneous predictions of the flow field. With the simplified approach introduced in this model, the Joule heating between the exit nozzle and the anode attachment position of the plasma arc is modeled by a volume heat source and the jet deflection caused by the anode processes by a momentum source at the anode surface. Furthermore, radiation effects are included by the net emission coefficient (NEC) method and diffusion is modeled with the combined diffusion coefficient method. The time-averaged simulation results are compared with numerous experimental measurements. The radial temperature profiles were obtained by spectroscopic measurements at different axial positions downstream of the exit nozzle. The velocity profiles were evaluated from the time-dependent evolution of flow structures, recorded by photodiode arrays. The shape of the plasma jet was compared with charge-coupled device (CCD) camera pictures. In the cooler regions, the temperature was measured by enthalpy probe downstream of the exit nozzle and by thermocouples in radial direction around the torch nozzle. The model results correspond well with the experimental measurements. The decrease in centerline temperature and velocity is predicted within an acceptable range and the shape of the jet closely resembles the jet structure in the recorded images. The temperatures at the edge of the jet are underestimated due to the absence of radial radiative heat transfer in the model.

Keywords: anode arc attachment, CFD modeling, experimental comparison, thermal plasma jet

Procedia PDF Downloads 367
66 Development and Evaluation of Economical Self-cleaning Cement

Authors: Anil Saini, Jatinder Kumar Ratan

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

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

Procedia PDF Downloads 172
65 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

Procedia PDF Downloads 132
64 Reflection of Landscape Agrogenization in the Soil Cover Structure and Profile Morphology: Example of Lithuania Agroecosystem

Authors: Jonas Volungevicius, Kristina Amaleviciute, Rimantas Vaisvalavicius, Alvyra Slepetiene, Darijus Veteikis

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Lithuanian territory is characterized by landscape with prevailing morain hills and clayey lowlands. The largest part of it has endured agrogenization of various degrees which was the cause of changes both in the structure of landscape and soil cover, transformations of soil profile and degradation of natural background soils. These changes influence negatively geoecological potential of landscape and soil and contribute to the weakening of the sustainability of agroecosystems. Research objective: to reveal the landscape agrogenization induced alterations of catenae and their appendant soil profiles in Lithuanian morain hills and clayey lowlands. Methods: Soil cover analysis and catenae charting was conducted using landscape profiling; soil morphology detected and soil type identified following WRB 2014. Granulometric composition of soil profiles was obtained by laser diffraction method (lazer diffractometer Mastersizer 2000). pH was measured in H2O extraction using potentiometric titration; SOC was determined by the Tyurin method modified by Nikitin, measuring with spectrometer Cary 50 (VARIAN) in 590 nm wavelength using glucose standards. Results: analysis showed that the decrease of forest vegetation and the other natural landscape components following the agrogenization of the research area influenced differently but significantly the structural alterations in soil cover and vertical soil profile. The research detected that due to landscape agrogenization, the suppression of zone-specific processes and the intensification of inter-zone processes determined by agrogenic factors take place in Lithuanian agroecosystems. In forested hills historically prevailing Retisols and Histosols territorial complex is transforming into the territorial complex of Regosols, Deluvial soils and drained Histosols. Processes taking place are simplification of vertical profile structure, intensive rejuvenation of profile, disappearance of the features of zone-specific soil-forming processes (podzolization, lessivage, gley formation). Erosion and deluvial processes manifest more intensively and weakly accumulating organic material more intensively spread in a vertical soil profile. The territorial soil complex of Gleyic Luvisols and Gleysols dominating in forested clayey lowlands subjected to agrogenization is transformed into the catena of drained Luvisols and pseudo Cambisols. The best expressed are their changes in moisture regime (morphological features of gley and stagnic properties are on decline) together with alterations of pH and distribution and intensity of accumulation of organic matter in profile. A specific horizon, antraquic, uncharacteristic to natural soil formation is appearing. Important to note that due to deep ploughing and other agrotechnical measures, the natural vertical differentiation of clay particles in a soil profile is destroyed which leads not only to alterations of physical qualities of soil, but also encumbers the identification of Luvisols by creating presumptions to misidentify them as Cambisols. The latter have never developed in these ecosystems under the present climatic conditions. Acknowledgements: This work was supported by the National Science Program: The effect of long-term, different-intensity management of resources on the soils of different genesis and on other components of the agro-ecosystems [grant number SIT-9/2015] funded by the Research Council of Lithuania.

Keywords: agroecosystems, landscape agrogenization, luvisols, retisols, transformation of soil profile

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63 Photophysics and Torsional Dynamics of Thioflavin T in Deep Eutectic Solvents

Authors: Rajesh Kumar Gautam, Debabrata Seth

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Thioflavin-T (ThT) play a key role of an important biologically active fluorescent sensor for amyloid fibrils. ThT molecule has been developed a method to detect the analysis of different type of diseases such as neurodegenerative disorders, Alzheimer’s, Parkinson’s, and type II diabetes. ThT was used as a fluorescent marker to detect the formation of amyloid fibril. In the presence of amyloid fibril, ThT becomes highly fluorescent. ThT undergoes twisting motion around C-C bonds of the two adjacent benzothiazole and dimethylaniline aromatic rings, which is predominantly affected by the micro-viscosity of the local environment. The present study articulates photophysics and torsional dynamics of biologically active molecule ThT in the presence of deep-eutectic solvents (DESs). DESs are environment-friendly, low cost and biodegradable alternatives to the ionic liquids. DES resembles ionic liquids, but the constituents of a DES include a hydrogen bond donor and acceptor species, in addition to ions. Due to the presence of the H-bonding network within a DES, it exhibits structural heterogeneity. Herein, we have prepared two different DESs by mixing urea with choline chloride and N, N-diethyl ethanol ammonium chloride at ~ 340 K. It was reported that deep eutectic mixture of choline chloride with urea gave a liquid with a freezing point of 12°C. We have experimented by taking two different concentrations of ThT. It was observed that at higher concentration of ThT (50 µM) it forms aggregates in DES. The photophysics of ThT as a function of temperature have been explored by using steady-state, and picoseconds time-resolved fluorescence emission spectroscopic techniques. From the spectroscopic analysis, we have observed that with rising temperature the fluorescence quantum yields and lifetime values of ThT molecule gradually decreases; this is the cumulative effect of thermal quenching and increase in the rate of the torsional rate constant. The fluorescence quantum yield and fluorescence lifetime decay values were always higher for DES-II (urea & N, N-diethyl ethanol ammonium chloride) than those for DES-I (urea & choline chloride). This was mainly due to the presence of structural heterogeneity of the medium. This was further confirmed by comparison with the activation energy of viscous flow with the activation energy of non-radiative decay. ThT molecule in less viscous media undergoes a very fast twisting process and leads to deactivation from the photoexcited state. In this system, the torsional motion increases with increasing temperature. We have concluded that beside bulk viscosity of the media, structural heterogeneity of the medium play crucial role to guide the photophysics of ThT in DESs. The analysis of the experimental data was carried out in the temperature range 288 ≤ T = 333K. The present articulate is to obtain an insight into the DESs as media for studying various photophysical processes of amyloid fibrils sensing molecule of ThT.

Keywords: deep eutectic solvent, photophysics, Thioflavin T, the torsional rate constant

Procedia PDF Downloads 163
62 Globalization of Pesticide Technology and Sustainable Agriculture

Authors: Gagandeep Kaur

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The pesticide industry is a big supplier of agricultural inputs. The uses of pesticides control weeds, fungal diseases, etc., which causes of yield losses in agricultural production. In agribusiness and agrichemical industry, Globalization of markets, competition and innovation are the dominant trends. By the tradition of increasing the productivity of agro-systems through generic, universally applicable technologies, innovation in the agrichemical industry is limited. The marketing of technology of agriculture needs to deal with some various trends such as locally-organized forces that envision regionalized sustainable agriculture in the future. Agricultural production has changed dramatically over the past century. Before World War second agricultural production was featured as a low input of money, high labor, mixed farming and low yields. Although mineral fertilizers were applied already in the second half of the 19th century, most f the crops were restricted by local climatic, geological and ecological conditions. After World War second, in the period of reconstruction, political and socioeconomic pressure changed the nature of agricultural production. For a growing population, food security at low prices and securing farmer income at acceptable levels became political priorities. Current agricultural policy the new European common agricultural policy is aimed to reduce overproduction, liberalization of world trade and the protection of landscape and natural habitats. Farmers have to increase the quality of their productivity and they have to control costs because of increased competition from the world market. Pesticides should be more effective at lower application doses, less toxic and not pose a threat to groundwater. There is a big debate taking place about how and whether to mitigate the intensive use of pesticides. This debate is about the future of agriculture which is sustainable agriculture. This is possible by moving away from conventional agriculture. Conventional agriculture is featured as high inputs and high yields. The use of pesticides in conventional agriculture implies crop production in a wide range. To move away from conventional agriculture is possible through the gradual adoption of less disturbing and polluting agricultural practices at the level of the cropping system. For a healthy environment for crop production in the future there is a need for the maintenance of chemical, physical or biological properties. There is also required to minimize the emission of volatile compounds in the atmosphere. Companies are limiting themselves to a particular interpretation of sustainable development, characterized by technological optimism and production-maximizing. So the main objective of the paper will present the trends in the pesticide industry and in agricultural production in the era of Globalization. The second objective is to analyze sustainable agriculture. Companies of pesticides seem to have identified biotechnology as a promising alternative and supplement to the conventional business of selling pesticides. The agricultural sector is in the process of transforming its conventional mode of operation. Some experts give suggestions to farmers to move towards precision farming and some suggest engaging in organic farming. The methodology of the paper will be historical and analytical. Both primary and secondary sources will be used.

Keywords: globalization, pesticides, sustainable development, organic farming

Procedia PDF Downloads 99
61 Simulation, Design, and 3D Print of Novel Highly Integrated TEG Device with Improved Thermal Energy Harvest Efficiency

Authors: Jaden Lu, Olivia Lu

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Despite the remarkable advancement of solar cell technology, the challenge of optimizing total solar energy harvest efficiency persists, primarily due to significant heat loss. This excess heat not only diminishes solar panel output efficiency but also curtails its operational lifespan. A promising approach to address this issue is the conversion of surplus heat into electricity. In recent years, there is growing interest in the use of thermoelectric generators (TEG) as a potential solution. The integration of efficient TEG devices holds the promise of augmenting overall energy harvest efficiency while prolonging the longevity of solar panels. While certain research groups have proposed the integration of solar cells and TEG devices, a substantial gap between conceptualization and practical implementation remains, largely attributed to low thermal energy conversion efficiency of TEG devices. To bridge this gap and meet the requisites of practical application, a feasible strategy involves the incorporation of a substantial number of p-n junctions within a confined unit volume. However, the manufacturing of high-density TEG p-n junctions presents a formidable challenge. The prevalent solution often leads to large device sizes to accommodate enough p-n junctions, consequently complicating integration with solar cells. Recently, the adoption of 3D printing technology has emerged as a promising solution to address this challenge by fabricating high-density p-n arrays. Despite this, further developmental efforts are necessary. Presently, the primary focus is on the 3D printing of vertically layered TEG devices, wherein p-n junction density remains constrained by spatial limitations and the constraints of 3D printing techniques. This study proposes a novel device configuration featuring horizontally arrayed p-n junctions of Bi2Te3. The structural design of the device is subjected to simulation through the Finite Element Method (FEM) within COMSOL Multiphysics software. Various device configurations are simulated to identify optimal device structure. Based on the simulation results, a new TEG device is fabricated utilizing 3D Selective laser melting (SLM) printing technology. Fusion 360 facilitates the translation of the COMSOL device structure into a 3D print file. The horizontal design offers a unique advantage, enabling the fabrication of densely packed, three-dimensional p-n junction arrays. The fabrication process entails printing a singular row of horizontal p-n junctions using the 3D SLM printing technique in a single layer. Subsequently, successive rows of p-n junction arrays are printed within the same layer, interconnected by thermally conductive copper. This sequence is replicated across multiple layers, separated by thermal insulating glass. This integration created in a highly compact three-dimensional TEG device with high density p-n junctions. The fabricated TEG device is then attached to the bottom of the solar cell using thermal glue. The whole device is characterized, with output data closely matching with COMSOL simulation results. Future research endeavors will encompass the refinement of thermoelectric materials. This includes the advancement of high-resolution 3D printing techniques tailored to diverse thermoelectric materials, along with the optimization of material microstructures such as porosity and doping. The objective is to achieve an optimal and highly integrated PV-TEG device that can substantially increase the solar energy harvest efficiency.

Keywords: thermoelectric, finite element method, 3d print, energy conversion

Procedia PDF Downloads 62
60 Assessment of On-Site Solar and Wind Energy at a Manufacturing Facility in Ireland

Authors: A. Sgobba, C. Meskell

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The feasibility of on-site electricity production from solar and wind and the resulting load management for a specific manufacturing plant in Ireland are assessed. The industry sector accounts directly and indirectly for a high percentage of electricity consumption and global greenhouse gas emissions; therefore, it will play a key role in emission reduction and control. Manufacturing plants, in particular, are often located in non-residential areas since they require open spaces for production machinery, parking facilities for the employees, appropriate routes for supply and delivery, special connections to the national grid and other environmental impacts. Since they have larger spaces compared to commercial sites in urban areas, they represent an appropriate case study for evaluating the technical and economic viability of energy system integration with low power density technologies, such as solar and wind, for on-site electricity generation. The available open space surrounding the analysed manufacturing plant can be efficiently used to produce a discrete quantity of energy, instantaneously and locally consumed. Therefore, transmission and distribution losses can be reduced. The usage of storage is not required due to the high and almost constant electricity consumption profile. The energy load of the plant is identified through the analysis of gas and electricity consumption, both internally monitored and reported on the bills. These data are not often recorded and available to third parties since manufacturing companies usually keep track only of the overall energy expenditures. The solar potential is modelled for a period of 21 years based on global horizontal irradiation data; the hourly direct and diffuse radiation and the energy produced by the system at the optimum pitch angle are calculated. The model is validated using PVWatts and SAM tools. Wind speed data are available for the same period within one-hour step at a height of 10m. Since the hub of a typical wind turbine reaches a higher altitude, complementary data for a different location at 50m have been compared, and a model for the estimate of wind speed at the required height in the right location is defined. Weibull Statistical Distribution is used to evaluate the wind energy potential of the site. The results show that solar and wind energy are, as expected, generally decoupled. Based on the real case study, the percentage of load covered every hour by on-site generation (Level of Autonomy LA) and the resulting electricity bought from the grid (Expected Energy Not Supplied EENS) are calculated. The economic viability of the project is assessed through Net Present Value, and the influence the main technical and economic parameters have on NPV is presented. Since the results show that the analysed renewable sources can not provide enough electricity, the integration with a cogeneration technology is studied. Finally, the benefit to energy system integration of wind, solar and a cogeneration technology is evaluated and discussed.

Keywords: demand, energy system integration, load, manufacturing, national grid, renewable energy sources

Procedia PDF Downloads 130
59 Potential Assessment and Techno-Economic Evaluation of Photovoltaic Energy Conversion System: A Case of Ethiopia Light Rail Transit System

Authors: Asegid Belay Kebede, Getachew Biru Worku

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The Earth and its inhabitants have faced an existential threat as a result of severe manmade actions. Global warming and climate change have been the most apparent manifestations of this threat throughout the world, with increasingly intense heat waves, temperature rises, flooding, sea-level rise, ice sheet melting, and so on. One of the major contributors to this disaster is the ever-increasing production and consumption of energy, which is still primarily fossil-based and emits billions of tons of hazardous GHG. The transportation industry is recognized as the biggest actor in terms of emissions, accounting for 24% of direct CO2 emissions and being one of the few worldwide sectors where CO2 emissions are still growing. Rail transportation, which includes all from light rail transit to high-speed rail services, is regarded as one of the most efficient modes of transportation, accounting for 9% of total passenger travel and 7% of total freight transit. Nonetheless, there is still room for improvement in the transportation sector, which might be done by incorporating alternative and/or renewable energy sources. As a result of these rapidly changing global energy situations and rapidly dwindling fossil fuel supplies, we were driven to analyze the possibility of renewable energy sources for traction applications. Even a small achievement in energy conservation or harnessing might significantly influence the total railway system and have the potential to transform the railway sector like never before. As a result, the paper begins by assessing the potential for photovoltaic (PV) power generation on train rooftops and existing infrastructure such as railway depots, passenger stations, traction substation rooftops, and accessible land along rail lines. As a result, a method based on a Google Earth system (using Helioscopes software) is developed to assess the PV potential along rail lines and on train station roofs. As an example, the Addis Ababa light rail transit system (AA-LRTS) is utilized. The case study examines the electricity-generating potential and economic performance of photovoltaics installed on AALRTS. As a consequence, the overall capacity of solar systems on all stations, including train rooftops, reaches 72.6 MWh per day, with an annual power output of 10.6 GWh. Throughout a 25-year lifespan, the overall CO2 emission reduction and total profit from PV-AA-LRTS can reach 180,000 tons and 892 million Ethiopian birrs, respectively. The PV-AA-LRTS has a 200% return on investment. All PV stations have a payback time of less than 13 years, and the price of solar-generated power is less than $0.08/kWh, which can compete with the benchmark price of coal-fired electricity. Our findings indicate that PV-AA-LRTS has tremendous potential, with both energy and economic advantages.

Keywords: sustainable development, global warming, energy crisis, photovoltaic energy conversion, techno-economic analysis, transportation system, light rail transit

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58 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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57 Biodegradation of Chlorophenol Derivatives Using Macroporous Material

Authors: Dmitriy Berillo, Areej K. A. Al-Jwaid, Jonathan L. Caplin, Andrew Cundy, Irina Savina

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Chlorophenols (CPs) are used as a precursor in the production of higher CPs and dyestuffs, and as a preservative. Contamination by CPs of the ground water is located in the range from 0.15-100mg/L. The EU has set maximum concentration limits for pesticides and their degradation products of 0.1μg/L and 0.5μg/L, respectively. People working in industries which produce textiles, leather products, domestic preservatives, and petrochemicals are most heavily exposed to CPs. The International Agency for Research on Cancers categorized CPs as potential human carcinogens. Existing multistep water purification processes for CPs such as hydrogenation, ion exchange, liquid-liquid extraction, adsorption by activated carbon, forward and inverse osmosis, electrolysis, sonochemistry, UV irradiation, and chemical oxidation are not always cost effective and can cause the formation of even more toxic or mutagenic derivatives. Bioremediation of CPs derivatives utilizing microorganisms results in 60 to 100% decontamination efficiency and the process is more environmentally-friendly compared with existing physico-chemical methods. Microorganisms immobilized onto a substrate show many advantages over free bacteria systems, such as higher biomass density, higher metabolic activity, and resistance to toxic chemicals. They also enable continuous operation, avoiding the requirement for biomass-liquid separation. The immobilized bacteria can be reused several times, which opens the opportunity for developing cost-effective processes for wastewater treatment. In this study, we develop a bioremediation system for CPs based on macroporous materials, which can be efficiently used for wastewater treatment. Conditions for the preparation of the macroporous material from specific bacterial strains (Pseudomonas mendocina and Rhodococus koreensis) were optimized. The concentration of bacterial cells was kept constant; the difference was only the type of cross-linking agents used e.g. glutaraldehyde, novel polymers, which were utilized at concentrations of 0.5 to 1.5%. SEM images and rheology analysis of the material indicated a monolithic macroporous structure. Phenol was chosen as a model system to optimize the function of the cryogel material and to estimate its enzymatic activity, since it is relatively less toxic and harmful compared to CPs. Several types of macroporous systems comprising live bacteria were prepared. The viability of the cross-linked bacteria was checked using Live/Dead BacLight kit and Laser Scanning Confocal Microscopy, which revealed the presence of viable bacteria with the novel cross-linkers, whereas the control material cross-linked with glutaraldehyde(GA), contained mostly dead cells. The bioreactors based on bacteria were used for phenol degradation in batch mode at an initial concentration of 50mg/L, pH 7.5 and a temperature of 30°C. Bacterial strains cross-linked with GA showed insignificant ability to degrade phenol and for one week only, but a combination of cross-linking agents illustrated higher stability, viability and the possibility to be reused for at least five weeks. Furthermore, conditions for CPs degradation will be optimized, and the chlorophenol degradation rates will be compared to those for phenol. This is a cutting-edge bioremediation approach, which allows the purification of waste water from sustainable compounds without a separation step to remove free planktonic bacteria. Acknowledgments: Dr. Berillo D. A. is very grateful to Individual Fellowship Marie Curie Program for funding of the research.

Keywords: bioremediation, cross-linking agents, cross-linked microbial cell, chlorophenol degradation

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56 Finite Element Method (FEM) Simulation, design and 3D Print of Novel Highly Integrated PV-TEG Device with Improved Solar Energy Harvest Efficiency

Authors: Jaden Lu, Olivia Lu

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Despite the remarkable advancement of solar cell technology, the challenge of optimizing total solar energy harvest efficiency persists, primarily due to significant heat loss. This excess heat not only diminishes solar panel output efficiency but also curtails its operational lifespan. A promising approach to address this issue is the conversion of surplus heat into electricity. In recent years, there is growing interest in the use of thermoelectric generators (TEG) as a potential solution. The integration of efficient TEG devices holds the promise of augmenting overall energy harvest efficiency while prolonging the longevity of solar panels. While certain research groups have proposed the integration of solar cells and TEG devices, a substantial gap between conceptualization and practical implementation remains, largely attributed to low thermal energy conversion efficiency of TEG devices. To bridge this gap and meet the requisites of practical application, a feasible strategy involves the incorporation of a substantial number of p-n junctions within a confined unit volume. However, the manufacturing of high-density TEG p-n junctions presents a formidable challenge. The prevalent solution often leads to large device sizes to accommodate enough p-n junctions, consequently complicating integration with solar cells. Recently, the adoption of 3D printing technology has emerged as a promising solution to address this challenge by fabricating high-density p-n arrays. Despite this, further developmental efforts are necessary. Presently, the primary focus is on the 3D printing of vertically layered TEG devices, wherein p-n junction density remains constrained by spatial limitations and the constraints of 3D printing techniques. This study proposes a novel device configuration featuring horizontally arrayed p-n junctions of Bi2Te3. The structural design of the device is subjected to simulation through the Finite Element Method (FEM) within COMSOL Multiphysics software. Various device configurations are simulated to identify optimal device structure. Based on the simulation results, a new TEG device is fabricated utilizing 3D Selective laser melting (SLM) printing technology. Fusion 360 facilitates the translation of the COMSOL device structure into a 3D print file. The horizontal design offers a unique advantage, enabling the fabrication of densely packed, three-dimensional p-n junction arrays. The fabrication process entails printing a singular row of horizontal p-n junctions using the 3D SLM printing technique in a single layer. Subsequently, successive rows of p-n junction arrays are printed within the same layer, interconnected by thermally conductive copper. This sequence is replicated across multiple layers, separated by thermal insulating glass. This integration created in a highly compact three-dimensional TEG device with high density p-n junctions. The fabricated TEG device is then attached to the bottom of the solar cell using thermal glue. The whole device is characterized, with output data closely matching with COMSOL simulation results. Future research endeavors will encompass the refinement of thermoelectric materials. This includes the advancement of high-resolution 3D printing techniques tailored to diverse thermoelectric materials, along with the optimization of material microstructures such as porosity and doping. The objective is to achieve an optimal and highly integrated PV-TEG device that can substantially increase the solar energy harvest efficiency.

Keywords: thermoelectric, finite element method, 3d print, energy conversion

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55 Optimizing Stormwater Sampling Design for Estimation of Pollutant Loads

Authors: Raja Umer Sajjad, Chang Hee Lee

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Stormwater runoff is the leading contributor to pollution of receiving waters. In response, an efficient stormwater monitoring program is required to quantify and eventually reduce stormwater pollution. The overall goals of stormwater monitoring programs primarily include the identification of high-risk dischargers and the development of total maximum daily loads (TMDLs). The challenge in developing better monitoring program is to reduce the variability in flux estimates due to sampling errors; however, the success of monitoring program mainly depends on the accuracy of the estimates. Apart from sampling errors, manpower and budgetary constraints also influence the quality of the estimates. This study attempted to develop optimum stormwater monitoring design considering both cost and the quality of the estimated pollutants flux. Three years stormwater monitoring data (2012 – 2014) from a mix land use located within Geumhak watershed South Korea was evaluated. The regional climate is humid and precipitation is usually well distributed through the year. The investigation of a large number of water quality parameters is time-consuming and resource intensive. In order to identify a suite of easy-to-measure parameters to act as a surrogate, Principal Component Analysis (PCA) was applied. Means, standard deviations, coefficient of variation (CV) and other simple statistics were performed using multivariate statistical analysis software SPSS 22.0. The implication of sampling time on monitoring results, number of samples required during the storm event and impact of seasonal first flush were also identified. Based on the observations derived from the PCA biplot and the correlation matrix, total suspended solids (TSS) was identified as a potential surrogate for turbidity, total phosphorus and for heavy metals like lead, chromium, and copper whereas, Chemical Oxygen Demand (COD) was identified as surrogate for organic matter. The CV among different monitored water quality parameters were found higher (ranged from 3.8 to 15.5). It suggests that use of grab sampling design to estimate the mass emission rates in the study area can lead to errors due to large variability. TSS discharge load calculation error was found only 2 % with two different sample size approaches; i.e. 17 samples per storm event and equally distributed 6 samples per storm event. Both seasonal first flush and event first flush phenomena for most water quality parameters were observed in the study area. Samples taken at the initial stage of storm event generally overestimate the mass emissions; however, it was found that collecting a grab sample after initial hour of storm event more closely approximates the mean concentration of the event. It was concluded that site and regional climate specific interventions can be made to optimize the stormwater monitoring program in order to make it more effective and economical.

Keywords: first flush, pollutant load, stormwater monitoring, surrogate parameters

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

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

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

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

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53 Polycyclic Aromatic Hydrocarbons: Pollution and Ecological Risk Assessment in Surface Soil of the Tezpur Town, on the North Bank of the Brahmaputra River, Assam, India

Authors: Kali Prasad Sarma, Nibedita Baul, Jinu Deka

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In the present study, pollution level of polycyclic aromatic hydrocarbon (PAH) in surface soil of historic Tezpur town located in the north bank of the River Brahmaputra were evaluated. In order to determine the seasonal distribution and concentration level of 16 USEPA priority PAHs surface soil samples were collected from 12 different sampling sites with various land use type. The total concentrations of 16 PAHs (∑16 PAHs) varied from 242.68µgkg-1to 7901.89µgkg-1. Concentration of total probable carcinogenic PAH ranged between 7.285µgkg-1 and 479.184 µgkg-1 in different seasons. However, the concentration of BaP, the most carcinogenic PAH, was found in the range of BDL to 50.01 µgkg-1. The composition profiles of PAHs in 3 different seasons were characterized by following two different types of ring: (1) 4-ring PAHs, contributed to highest percentage of total PAHs (43.75%) (2) while in pre- and post- monsoon season 3- ring compounds dominated the PAH profile, contributing 65.58% and 74.41% respectively. A high PAHs concentration with significant seasonality and high abundance of LMWPAHs was observed in Tezpur town. Soil PAHs toxicity was evaluated taking toxic equivalency factors (TEFs), which quantify the carcinogenic potential of other PAHs relative to BaP and estimate benzo[a]pyrene-equivalent concentration (BaPeq). The calculated BaPeq value signifies considerable risk to contact with soil PAHs. We applied cluster analysis and principal component analysis (PCA) with multivariate linear regression (MLR) to apportion sources of polycyclic aromatic hydrocarbons (PAHs) in surface soil of Tezpur town, based on the measured PAH concentrations. The results indicate that petrogenic and pyrogenic sources are the important sources of PAHs. A combination of chemometric and molecular indices were used to identify the sources of PAHs, which could be attributed to vehicle emissions, a mixed source input, natural gas combustion, wood or biomass burning and coal combustion. Source apportionment using absolute principle component scores–multiple linear regression showed that the main sources of PAHs are 22.3% mix sources comprising of diesel and biomass combustion and petroleum spill,13.55% from vehicle emission, 9.15% from diesel and natural gas burning, 38.05% from wood and biomass burning and 16.95% contribute coal combustion. Pyrogenic input was found to dominate source of PAHs origin with more contribution from vehicular exhaust. PAHs have often been found to co-emit with other environmental pollutants like heavy metals due to similar source of origin. A positive correlation was observed between PAH with Cr and Pb (r2 = 0.54 and 0.55 respectively) in monsoon season and PAH with Cd and Pb (r2 = 0.54 and 0.61 respectively) indicating their common source. Strong correlation was observed between PAH and OC during pre- and post- monsoon (r2=0.46 and r2=0.65 respectively) whereas during monsoon season no significant correlation was observed (r2=0.24).

Keywords: polycyclic aromatic hydrocarbon, Tezpur town, chemometric analysis, ecological risk assessment, pollution

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52 Multi-Criteria Decision Making Network Optimization for Green Supply Chains

Authors: Bandar A. Alkhayyal

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Modern supply chains are typically linear, transforming virgin raw materials into products for end consumers, who then discard them after use to landfills or incinerators. Nowadays, there are major efforts underway to create a circular economy to reduce non-renewable resource use and waste. One important aspect of these efforts is the development of Green Supply Chain (GSC) systems which enables a reverse flow of used products from consumers back to manufacturers, where they can be refurbished or remanufactured, to both economic and environmental benefit. This paper develops novel multi-objective optimization models to inform GSC system design at multiple levels: (1) strategic planning of facility location and transportation logistics; (2) tactical planning of optimal pricing; and (3) policy planning to account for potential valuation of GSC emissions. First, physical linear programming was applied to evaluate GSC facility placement by determining the quantities of end-of-life products for transport from candidate collection centers to remanufacturing facilities while satisfying cost and capacity criteria. Second, disassembly and remanufacturing processes have received little attention in industrial engineering and process cost modeling literature. The increasing scale of remanufacturing operations, worth nearly $50 billion annually in the United States alone, have made GSC pricing an important subject of research. A non-linear physical programming model for optimization of pricing policy for remanufactured products that maximizes total profit and minimizes product recovery costs were examined and solved. Finally, a deterministic equilibrium model was used to determine the effects of internalizing a cost of GSC greenhouse gas (GHG) emissions into optimization models. Changes in optimal facility use, transportation logistics, and pricing/profit margins were all investigated against a variable cost of carbon, using case study system created based on actual data from sites in the Boston area. As carbon costs increase, the optimal GSC system undergoes several distinct shifts in topology as it seeks new cost-minimal configurations. A comprehensive study of quantitative evaluation and performance of the model has been done using orthogonal arrays. Results were compared to top-down estimates from economic input-output life cycle assessment (EIO-LCA) models, to contrast remanufacturing GHG emission quantities with those from original equipment manufacturing operations. Introducing a carbon cost of $40/t CO2e increases modeled remanufacturing costs by 2.7% but also increases original equipment costs by 2.3%. The assembled work advances the theoretical modeling of optimal GSC systems and presents a rare case study of remanufactured appliances.

Keywords: circular economy, extended producer responsibility, greenhouse gas emissions, industrial ecology, low carbon logistics, green supply chains

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