Search results for: fiber measurements

Authors: Sherif Keddis, Rafik Mitry, Norbert Schwesinger

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Intelligent networking of devices has rapidly been gaining importance over the past years and with recent advances in the fields of microcontrollers, integrated circuits and wireless communication, low power applications have emerged, enabling this trend even more. Connected devices provide a much larger database thus enabling highly intelligent and accurate systems. Ensuring safe drinking water is one of the fields that require constant monitoring and can benefit from an increased accuracy. Monitoring is mainly achieved either through complex measures, such as collecting samples from the points of use, or through metering systems typically distant to the points of use which deliver less accurate assessments of the quality of water. Constant metering near the points of use is complicated due to their inaccessibility; e.g. buried water pipes, locked spaces, which makes system maintenance extremely difficult and often unviable. The research presented here attempts to overcome this challenge by providing these systems with enough energy through a flow harvester inside the pipe thus eliminating the maintenance requirements in terms of battery replacements or containment of leakage resulting from wiring such systems. The proposed flow harvester exploits the piezoelectric properties of polyvinylidene difluoride (PVDF) films to convert turbulence induced oscillations into electrical energy. It is intended to be used in standard water pipes with diameters between 0.5 and 1 inch. The working principle of the harvester uses a ring shaped bluff body inside the pipe to induce pressure fluctuations. Additionally the bluff body houses electronic components such as storage, circuitry and RF-unit. Placing the piezoelectric films downstream of that bluff body causes their oscillation which generates electrical charge. The PVDF-film is placed as a multilayered wrap fixed to the pipe wall leaving the top part to oscillate freely inside the flow. The warp, which allows for a larger active, consists of two layers of 30µm thick and 12mm wide PVDF layered alternately with two centered 6µm thick and 8mm wide aluminum foil electrodes. The length of the layers depends on the number of windings and is part of the investigation. Sealing the harvester against liquid penetration is achieved by wrapping it in a ring-shaped LDPE-film and welding the open ends. The fabrication of the PVDF-wraps is done by hand. After validating the working principle using a wind tunnel, experiments have been conducted in water, placing the harvester inside a 1 inch pipe at water velocities of 0.74m/s. To find a suitable placement of the wrap inside the pipe, two forms of fixation were compared regarding their power output. Further investigations regarding the number of windings required for efficient transduction were made. Best results were achieved using a wrap with 3 windings of the active layers which delivers a constant power output of 0.53µW at a 2.3MΩ load and an effective voltage of 1.1V. Considering the extremely low power requirements of sensor applications, these initial results are promising. For further investigations and optimization, machine designs are currently being developed to automate the fabrication and decrease tolerance of the prototypes.

Keywords: maintenance-free sensors, measurements at point of use, piezoelectric flow harvesting, universal micro generator, wireless metering systems

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Authors: Andreea Campu, Ilinica Muresan, Simona Cainap, Simion Astilean, Monica Focsan

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Acute myocardial infarction (AMI) is the most severe cardiovascular disease, which has threatened human lives for decades, thus a continuous interest is directed towards the detection of cardiac biomarkers such as cardiac troponin I (cTnI) in order to predict risk and, implicitly, fulfill the early diagnosis requirements in AMI settings. Microfluidics is a major technology involved in the development of efficient sensing devices with real-time fast responses and on-site applicability. Microfluidic devices have gathered a lot of attention recently due to their advantageous features such as high sensitivity and specificity, miniaturization and portability, ease-of-use, low-cost, facile fabrication, and reduced sample manipulation. The integration of gold nanoparticles into the structure of microfluidic sensors has led to the development of highly effective detection systems, considering the unique properties of the metallic nanostructures, specifically the Localized Surface Plasmon Resonance (LSPR), which makes them highly sensitive to their microenvironment. In this scientific context, herein, we propose the implementation of a novel detection device, which successfully combines the efficiency of gold bipyramids (AuBPs) as signal transducers and thermal generators with the sample-driven advantages of the microfluidic channels into a miniaturized, portable, low-cost, specific, and sensitive test for the dual LSPR-thermographic cTnI detection. Specifically, AuBPs with longitudinal LSPR response at 830 nm were chemically synthesized using the seed-mediated growth approach and characterized in terms of optical and morphological properties. Further, the colloidal AuBPs were deposited onto pre-treated silanized glass substrates thus, a uniform nanoparticle coverage of the substrate was obtained and confirmed by extinction measurements showing a 43 nm blue-shift of the LSPR response as a consequence of the refractive index change. The as-obtained plasmonic substrate was then integrated into a microfluidic “Y”-shaped polydimethylsiloxane (PDMS) channel, fabricated using a Laser Cutter system. Both plasmonic and microfluidic elements were plasma treated in order to achieve a permanent bond. The as-developed microfluidic plasmonic chip was further coupled to an automated syringe pump system. The proposed biosensing protocol implicates the successive injection inside the microfluidic channel as follows: p-aminothiophenol and glutaraldehyde, to achieve a covalent bond between the metallic surface and cTnI antibody, anti-cTnI, as a recognition element, and target cTnI biomarker. The successful functionalization and capture of cTnI was monitored by LSPR detection thus, after each step, a red-shift of the optical response was recorded. Furthermore, as an innovative detection technique, thermal determinations were made after each injection by exposing the microfluidic plasmonic chip to 785 nm laser excitation, considering that the AuBPs exhibit high light-to-heat conversion performances. By the analysis of the thermographic images, thermal curves were obtained, showing a decrease in the thermal efficiency after the anti-cTnI-cTnI reaction was realized. Thus, we developed a microfluidic plasmonic chip able to operate as both LSPR and thermal sensor for the detection of the cardiac troponin I biomarker, leading thus to the progress of diagnostic devices.

Keywords: gold nanobipyramids, microfluidic device, localized surface plasmon resonance detection, thermographic detection

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Authors: Mohamed Gazzeh, Bradley Null, Fethi Tlili, Hichem Besbes

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The burgeoning global ownership of personal vehicles has posed a significant strain on urban infrastructure, notably parking facilities, leading to traffic congestion and environmental concerns. Effective parking management systems (PMS) are indispensable for optimizing urban traffic flow and reducing emissions. The most commonly deployed systems nowadays rely on computer vision technology. This paper explores the integration of radar sensors and simulation in the context of smart parking management. We concentrate on radar sensors due to their versatility and utility in automotive applications, which extends to PMS. Additionally, radar sensors play a crucial role in driver assistance systems and autonomous vehicle development. However, the resource-intensive nature of radar data collection for algorithm development and testing necessitates innovative solutions. Simulation, particularly the monoDrive simulator, an internal development tool used by NI the Test and Measurement division of Emerson, offers a practical means to overcome this challenge. The primary objectives of this study encompass simulating radar sensors to generate a substantial dataset for algorithm development, testing, and, critically, assessing the transferability of models between simulated and real radar data. We focus on occupancy detection in parking as a practical use case, categorizing each parking space as vacant or occupied. The simulation approach using monoDrive enables algorithm validation and reliability assessment for virtual radar sensors. It meticulously designed various parking scenarios, involving manual measurements of parking spot coordinates, orientations, and the utilization of TI AWR1843 radar. To create a diverse dataset, we generated 4950 scenarios, comprising a total of 455,400 parking spots. This extensive dataset encompasses radar configuration details, ground truth occupancy information, radar detections, and associated object attributes such as range, azimuth, elevation, radar cross-section, and velocity data. The paper also addresses the intricacies and challenges of real-world radar data collection, highlighting the advantages of simulation in producing radar data for parking lot applications. We developed classification models based on Support Vector Machines (SVM) and Density-Based Spatial Clustering of Applications with Noise (DBSCAN), exclusively trained and evaluated on simulated data. Subsequently, we applied these models to real-world data, comparing their performance against the monoDrive dataset. The study demonstrates the feasibility of transferring models from a simulated environment to real-world applications, achieving an impressive accuracy score of 92% using only one radar sensor. This finding underscores the potential of radar sensors and simulation in the development of smart parking management systems, offering significant benefits for improving urban mobility and reducing environmental impact. The integration of radar sensors and simulation represents a promising avenue for enhancing smart parking management systems, addressing the challenges posed by the exponential growth in personal vehicle ownership. This research contributes valuable insights into the practicality of using simulated radar data in real-world applications and underscores the role of radar technology in advancing urban sustainability.

Keywords: autonomous vehicle simulator, FMCW radar sensors, occupancy detection, smart parking management, transferability of models

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Authors: Todd H. Buxton, Yong G. Lai

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Temperature management in regulated rivers can involve significant expenditures of water to meet the cold-water requirements of species in summer. For this purpose, flows released from Lewiston Dam on the Trinity River in Northern California are 12.7 cms with temperatures around 11oC in July through September to provide adult spring Chinook cold water to hold in deep pools and mature until spawning in fall. The releases are more than double the flow and 10oC colder temperatures than the natural conditions before the dam was built. The high, cold releases provide springers the habitat they require but may suppress the stream food base and limit future populations of salmon by reducing the juvenile fish size and survival to adults via the positive relationship between the two. Field and modeling research was undertaken to explore whether lowering summer releases from Lewiston Dam may promote thermal stratification in river pools so that both the cold-water needs of adult salmon and warmer water requirements of other organisms in the stream biome may be met. For this investigation, a three-dimensional (3D) computational fluid dynamics (CFD) model was developed and validated with field measurements in two deep pools on the Trinity River. Modeling and field observations were then used to identify the flows and temperatures that may form and maintain thermal stratification under different meteorologic conditions. Under low flows, a pool was found to be well mixed and thermally homogenous until temperatures began to stratify shortly after sunrise. Stratification then strengthened through the day until shading from trees and mountains cooled the inlet flow and decayed the thermal gradient, which collapsed shortly before sunset and returned the pool to a well-mixed state. This diurnal process of stratification formation and destruction was closely predicted by the 3D CFD model. Both the model and field observations indicate that thermal stratification maintained the coldest temperatures of the day at ≥2m depth in a pool and provided water that was around 8oC warmer in the upper 2m of the pool. Results further indicate that the stratified pool under low flows provided almost the same daily average temperatures as when flows were an order of magnitude higher and stratification was prevented, indicating significant water savings may be realized in regulated streams while also providing a diversity in water temperatures the ecosystem requires. With confidence in the 3D CFD model, the model is now being applied to a dozen pools in the Trinity River to understand how pool bathymetry influences thermal stratification under variable flows and diurnal temperature variations. This knowledge will be used to expand the results to 52 pools in a 64 km reach below Lewiston Dam that meet the depth criteria (≥2 m) for spring Chinook holding. From this, rating curves will be developed to relate discharge to the volume of pool habitat that provides springers the temperature (<15.6oC daily average), velocity (0.15 to 0.4 m/s) and depths that accommodate the escapement target for spring Chinook (6,000 adults) under maximum fish densities measured in other streams (3.1 m3/fish) during the holding time of year (May through August). Flow releases that meet these goals will be evaluated for water savings relative to the current flow regime and their influence on indicator species, including the Foothill Yellow-Legged Frog, and aspects of the stream biome that support salmon populations, including macroinvertebrate production and juvenile Chinook growth rates.

Keywords: 3D CFD modeling, flow regulation, thermal stratification, chinook salmon, foothill yellow-legged frogs, water managment

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Authors: Juergen Orasche, Vesta Kohlmeier, George C. Dragan, Gert Jakobi, Patricia Forbes, Ralf Zimmermann

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Underground mining poses a difficult environment for both man and machines. At more than 1000 meters underneath the surface of the earth, ores and other mineral resources are still gained by conventional and motorised mining. Adding to the hazards caused by blasting and stone-chipping, the working conditions are best described by the high temperatures of 35-40°C and high humidity, at low air exchange rates. Separate ventilation shafts lead fresh air into a mine and others lead expended air back to the surface. This is essential for humans and machines working deep underground. Nevertheless, mines are widely ramified. Thus the air flow rate at the far end of a tunnel is sensed to be close to zero. In recent years, conventional mining was supplemented by mining with heavy diesel machines. These very flat machines called Load Haul Dump (LHD) vehicles accelerate and ease work in areas favourable for heavy machines. On the other hand, they emit non-filtered diesel exhaust, which constitutes an occupational hazard for the miners. Combined with a low air exchange, high humidity and inorganic dust from the mining it leads to 'black smog' underneath the earth. This work focuses on the air quality in mines employing LHDs. Therefore we performed personal sampling (samplers worn by miners during their work), stationary sampling and aethalometer (Microaeth MA200, Aethlabs) measurements in a platinum mine in around 1000 meters under the earth’s surface. We compared areas of high diesel exhaust emission with areas of conventional mining where no diesel machines were operated. For a better assessment of health risks caused by air pollution we applied a separated gas-/particle-sampling tool (or system), with first denuder section collecting intermediate VOCs. These multi-channel silicone rubber denuders are able to trap IVOCs while allowing particles ranged from 10 nm to 1 µm in diameter to be transmitted with an efficiency of nearly 100%. The second section is represented by a quartz fibre filter collecting particles and adsorbed semi-volatile organic compounds (SVOC). The third part is a graphitized carbon black adsorber – collecting the SVOCs that evaporate from the filter. The compounds collected on these three sections were analyzed in our labs with different thermal desorption techniques coupled with gas chromatography and mass spectrometry (GC-MS). VOCs and IVOCs were measured with a Shimadzu Thermal Desorption Unit (TD20, Shimadzu, Japan) coupled to a GCMS-System QP 2010 Ultra with a quadrupole mass spectrometer (Shimadzu). The GC was equipped with a 30m, BP-20 wax column (0.25mm ID, 0.25µm film) from SGE (Australia). Filters were analyzed with In-situ derivatization thermal desorption gas chromatography time-of-flight-mass spectrometry (IDTD-GC-TOF-MS). The IDTD unit is a modified GL sciences Optic 3 system (GL Sciences, Netherlands). The results showed black carbon concentrations measured with the portable aethalometers up to several mg per m³. The organic chemistry was dominated by very high concentrations of alkanes. Typical diesel engine exhaust markers like alkylated polycyclic aromatic hydrocarbons were detected as well as typical lubrication oil markers like hopanes.

Keywords: diesel emission, personal sampling, aethalometer, mining

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Authors: Faranak Felfeliyan, Parvaneh Shokrani, Maryam Atarod

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Introduction Using electron beam is widespread in radiotherapy. The main criteria in radiation therapy is to irradiate the tumor volume with maximum prescribed dose and minimum dose to vital organs around it. Using abutting fields is common in radiotherapy. The main problem in using abutting fields is dose inhomogeneity in the junction region. Electron beam divergence and lateral scattering may lead to hot and cold spots in the junction region. One solution for this problem is using of a spoiler to broaden the penumbra and uniform dose in the junction region. The goal of this research was to compare titanium and aluminum effects as a spoiler for dose uniformity achievement in the junction region of oblique electron fields with Monte Carlo simulation. Dose uniformity in the junction region depends on density, scattering power, thickness of the spoiler and the angle between two fields. Materials and Methods In this study, Monte Carlo model of Siemens Primus linear accelerator was simulated for a 5 MeV nominal energy electron beam using manufacture provided specifications. BEAMnrc and EGSnrc user code were used to simulate the treatment head in electron mode (simulation of beam model). The resulting phase space file was used as a source for dose calculations for 10×10 cm2 field size at SSD=100 cm in a 30×30×45 cm3 water phantom using DOSXYZnrc user code (dose calculations). An automatic MP3-M water phantom tank, MEPHYSTO mc2 software platform and a Semi-Flex Chamber-31010 with sensitive vol­ume of 0.125 cm3 (PTW, Freiburg, Germany) were used for dose distribution measurements. Moreover, the electron field size was 10×10 cm2 and SSD=100 cm. Validation of devel­oped beam model was done by comparing the measured and calculated depth and lateral dose distributions (verification of electron beam model). Simulation of spoilers (using SLAB compo­nent module) placed at the end of the electron applicator, was done using previously vali­dated phase space file for a 5 MeV nominal energy and 10×10 cm2 field size (simulation of spoiler). An in-house routine was developed in order to calculate the combined isodose curves re­sulting from the two simulated abutting fields (calculation of dose distribution in abutting electron fields). Results Verification of the developed 5.9 MeV elec­tron beam model was done by comparing the calculated and measured dose distributions. The maximum percentage difference between calculated and measured PDD was 1%, except for the build-up region in which the difference was 2%. The difference between calculated and measured profile was 2% at the edges of the field and less than 1% in other regions. The effect of PMMA, aluminum, titanium and chromium in dose uniformity achievement in abutting normal electron fields with equivalent thicknesses to 5mm PMMA was evaluated. Comparing R90 and uniformity index of different materials, aluminum was chosen as the optimum spoiler. Titanium has the maximum surface dose. Thus, aluminum and titanium had been chosen to use for dose uniformity achievement in oblique electron fields. Using the optimum beam spoiler, junction dose decreased from 160% to 110% for 15 degrees, from 180% to 120% for 30 degrees, from 160% to 120% for 45 degrees and from 180% to 100% for 60 degrees oblique abutting fields. Using Titanium spoiler, junction dose decreased from 160% to 120% for 15 degrees, 180% to 120% for 30 degrees, 160% to 120% for 45 degrees and 180% to 110% for 60 degrees. In addition, penumbra width for 15 degrees, without spoiler in the surface was 10 mm and was increased to 15.5 mm with titanium spoiler. For 30 degrees, from 9 mm to 15 mm, for 45 degrees from 4 mm to 6 mm and for 60 degrees, from 5 mm to 8 mm. Conclusion Using spoilers, penumbra width at the surface increased, size and depth of hot spots was decreased and dose homogeneity improved at the junc­tion of abutting electron fields. Dose at the junction region of abutting oblique fields was improved significantly by using spoiler. Maximum dose at the junction region for 15⁰, 30⁰, 45⁰ and 60⁰ was decreased about 40%, 60%, 40% and 70% respectively for Titanium and about 50%, 60%, 40% and 80% for Aluminum. Considering significantly decrease in maximum dose using titanium spoiler, unfortunately, dose distribution in the junction region was not decreased less than 110%.

Keywords: abutting fields, electron beam, radiation therapy, spoilers

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Authors: S. Fadda, M. Fiori, C. Matzuzzi

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Mineralized formations in the bottom sediments of a Miocene transgression have been discovered in Sardinia. The mineral assemblage consists of copper sulphides and oxidates suggesting fluctuations of redox conditions in neutral to high-pH restricted shallow-water coastal basins. Azurite/malachite has been observed as authigenic and occurs as loose spheroidal crystalline particles associated with the transitional-littoral horizon forming the bottom of the marine transgression. Many field observations are consistent with a supergenic circulation of metals involving terrestrial groundwater-seawater mixing. Both clastic materials and metals come from Tertiary volcanic edifices while the main precipitating anions, carbonates, and sulphides species are of both continental and marine origin. Formation of Cu carbonates as a supergene secondary 'oxide' assemblage, does not agree with field evidences, petrographic observations along with textural evidences in the host-rock types. Samples were collected along the sedimentary sequence for different analyses: the majority of elements were determined by X-ray fluorescence and plasma-atomic emission spectroscopy. Mineral identification was obtained by X-ray diffractometry and scanning electron microprobe. Thin sections of the samples were examined in microscopy while porosity measurements were made using a mercury intrusion porosimeter. Cu-carbonates deposited at a temperature below 100 C° which is consistent with the clay minerals in the matrix of the host rock dominated by illite and montmorillonite. Azurite nodules grew during the early diagenetic stage through reaction of cupriferous solutions with CO₂ imported from the overlying groundwater and circulating through the sandstones during shallow burial. Decomposition of organic matter in the bottom anoxic waters released additional carbon dioxide to pore fluids for azurite stability. In this manner localized reducing environments were also generated in which Cu was fixed as Cu-sulphide and sulphosalts. Microscopic examinations of textural features of azurite nodules give evidence of primary malachite/azurite deposition rather than supergene oxidation in place of primary sulfides. Photomicrographs show nuclei of azurite and malachite surrounded by newly formed microcrystalline carbonates which constitute the matrix. The typical pleochroism of crystals can be observed also when this mineral fills microscopic fissures or cracks. Sedimentological evidence of transgression and regression indicates that the pore water would have been a variable mixture of marine water and groundwaters with a possible meteoric component in an alternatively exposed and subaqueous environment owing to water-level fluctuation. Salinity data of the pore fluids, assessed at random intervals along the mineralised strata confirmed the values between about 7000 and 30,000 ppm measured in coeval sediments at the base of Miocene falling in the range of a more or less diluted sea water. This suggests a variation in mean pore-fluids pH between 5.5 and 8.5, compatible with the oxidized and reduced mineral paragenesis described in this work. The results of stable isotopes studies reflect the marine transgressive-regressive cyclicity of events and are compatibile with carbon derivation from sea water. During the last oxidative stage of diagenesis, under surface conditions of higher activity of H₂O and O₂, CO₂ partial pressure decreased, and malachite becomes the stable Cu mineral. The potential for these small but high grade deposits does exist.

Keywords: sedimentary, Cu-carbonates, authigenic, tertiary, Sardinia

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Authors: Joyjit Dey, Souvik Sen

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Middle Permian Barakar formation is the major economic coal bearing unit of vast east-west trending Damodar Valley basin of Gondwana coalfield. Primary sedimentary structures were studied from the core holes, which represent majorly four facies groups: sandstone dominated facies, sandstone-shale heterolith facies, shale facies and coal facies. Total eight major coal seams have been identified with the bottom most seam being the thickest. Laterally, continuous coal seams were deposited in the calm and quiet environment of extensive floodplain swamps. Channel sinuosity and lateral channel migration/avulsion results in lateral facies heterogeneity and coal splitting. Geophysical well logs (Gamma-Resistivity-Density logs) have been used to establish the vertical and lateral correlation of various litho units field-wide, which reveals the predominance of repetitive fining upwards cycles. Well log data being a permanent record, offers a strong foundation for generating log based property evaluation and helps in characterization of depositional units in terms of lateral and vertical heterogeneity. Low gamma, high resistivity, low density is the typical coal seam signatures in geophysical logs. Here, we have used a density cutoff of 1.6 g/cc as a primary discriminator of coal and the same has been employed to compute various coal assay parameters, which are ash, fixed carbon, moisture, volatile content, cleat porosity, vitrinite reflectance (VRo%), which were calibrated with the laboratory based measurements. The study shows ash content and VRo% increase from west to east (towards basin margin), while fixed carbon, moisture and volatile content increase towards west, depicting increased coal quality westwards. Seam wise cleat porosity decreases from east to west, this would be an effect of overburden, as overburden pressure increases westward with the deepening of basin causing more sediment packet deposited on the western side of the study area. Coal is a porous, viscoelastic material in which velocity and strain both change nonlinearly with stress, especially for stress applied perpendicular to the bedding plane. Usually, the coal seam has a high velocity contrast relative to its neighboring layers. Despite extensive discussion of the maceral and chemical properties of coal, its elastic characteristics have received comparatively little attention. The measurement of the elastic constants of coal presents many difficulties: sample-to-sample inhomogeneity and fragility and velocity dependence on stress, orientation, humidity, and chemical content. In this study, a conclusive empirical equation VS= 0.80VP-0.86 has been used to model shear velocity from compression velocity. Also the same has been used to compute various geomechanical moduli. Geomech analyses yield a Poisson ratio of 0.348 against coals. Average bulk modulus value is 3.97 GPA, while average shear modulus and Young’s modulus values are coming out as 1.34 and 3.59 GPA respectively. These middle Permian Barakar coals show an average 23.84 MPA uniaxial compressive strength (UCS) with 4.97 MPA cohesive strength and 0.46 as friction coefficient. The output values of log based proximate parameters and geomechanical moduli suggest a medium volatile Bituminous grade for the studied coal seams, which is found in the laboratory based core study as well.

Keywords: core analysis, coal characterization, geophysical log, geo-mechanical moduli

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Authors: Christian J. Kennett, Mark A. Baldwin

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As several companies are working towards returning American astronauts back to space on US-made spacecraft, NASA developed a human flight certification-by-test and analysis approach due to the cost-prohibitive nature of extensive testing. This process relies heavily on the quality of analytical models to accurately predict crew injury potential specific to each spacecraft and under dynamic environments not tested. As the prime contractor on the Orion spacecraft, Lockheed Martin was tasked with quantifying the correlation of analytical anthropometric test devices (ATDs), also known as crash test dummies, against test measurements under representative impact conditions. Multiple dynamic impact sled tests were conducted to characterize Hybrid III 5th ATD lumbar, head, and neck responses with and without a modified shuttle-era advanced crew escape suit (ACES) under simulated Orion landing and abort conditions. Each ATD was restrained via a 5-point harness in a mockup Orion seat fixed to a dynamic impact sled at the Wright Patterson Air Force Base (WPAFB) Biodynamics Laboratory in the horizontal impact accelerator (HIA). ATDs were subject to multiple impact magnitudes, half-sine pulse rise times, and XZ - ‘eyeballs out/down’ or Z-axis ‘eyeballs down’ orientations for landing or an X-axis ‘eyeballs in’ orientation for abort. Several helmet constraint devices were evaluated during suited testing. Unique finite element models (FEMs) were developed of the unsuited and suited sled test configurations using an analytical 5th ATD model developed by LSTC (Livermore, CA) and deformable representations of the seat, suit, helmet constraint countermeasures, and body restraints. Explicit FE analyses were conducted using the non-linear solver LS-DYNA. Head linear and rotational acceleration, head rotational velocity, upper neck force and moment, and lumbar force time histories were compared between test and analysis using the enhanced error assessment of response time histories (EEARTH) composite score index. The EEARTH rating paired with the correlation and analysis (CORA) corridor rating provided a composite ISO score that was used to asses model correlation accuracy. NASA occupant protection subject matter experts established an ISO score of 0.5 or greater as the minimum expectation for correlating analytical and experimental ATD responses. Unsuited 5th ATD head X, Z, and resultant linear accelerations, head Y rotational accelerations and velocities, neck X and Z forces, and lumbar Z forces all showed consistent ISO scores above 0.5 in the XZ impact orientation, regardless of peak g-level or rise time. Upper neck Y moments were near or above the 0.5 score for most of the XZ cases. Similar trends were found in the XZ and Z-axis suited tests despite the addition of several different countermeasures for restraining the helmet. For the X-axis ‘eyeballs in’ loading direction, only resultant head linear acceleration and lumbar Z-axis force produced ISO scores above 0.5 whether unsuited or suited. The analytical LSTC 5th ATD model showed good correlation across multiple head, neck, and lumbar responses in both the unsuited and suited configurations when loaded in the XZ ‘eyeballs out/down’ direction. Upper neck moments were consistently the most difficult to predict, regardless of impact direction or test configuration.

Keywords: impact biomechanics, manned spaceflight, model correlation, multi-axial loading

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Authors: Priyanka Botny Srinath, Alessandro Suglia, Mel McKendrick

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Background: Organizational cultural studies integrate sociology and anthropology, portraying man as a creator of symbols, languages, beliefs, and ideologies -essentially, a creator and manager of meaning. In our research, we leverage analytical measures to discern whether an organization embodies a singular culture or a myriad of subcultures. Fast-forward to 2023, our research thesis focuses on digitally measuring culture, coining it as the "Work Culture Quotient." This entails conceptually mapping common experiential patterns to provide executives insights into the digital organization journey, aiding in understanding their current position and identifying future steps. Objectives: Finding the new age skills that help in defining the culture; understand the implications of post-COVID effects; derive a digital framework for measuring skillsets. Method: We conducted two comprehensive Delphi studies to distill essential insights. Delphi 1: Through a thematic analysis of interviews with 20 high-level leaders representing companies across diverse regions -India, Japan, the US, Canada, Morocco, and Uganda- we identified 20 key skills critical for cultivating a robust organizational culture. The skills are -influence, self-confidence, optimism, empathy, leadership, collaboration and cooperation, developing others, commitment, innovativeness, leveraging diversity, change management, team capabilities, self-control, digital communication, emotional awareness, team bonding, communication, problem solving, adaptability, and trustworthiness. Delphi 2: Subject matter experts were asked to complete a questionnaire derived from the thematic analysis in stage 1 to formalise themes and draw consensus amongst experts on the most important workplace skills. Results: The thematic analysis resulted in 20 workplace employee skills being identified. These skills were all included in the Delphi round 2 questionnaire. From the outputs, we analysed the data using R Studio for arriving at agreement and consensus, we also used sum of squares method to compare various agreements to extract various themes with a threshold of 80% agreements. This yielded three themes at over 80% agreement (leadership, collaboration and cooperation, communication) and three further themes at over 60% agreement (commitment, empathy, trustworthiness). From this, we selected five questionnaires to be included in the primary data collection phase, and these will be paired with the digital footprints to provide a workplace culture quotient. Implications: The findings from these studies bear profound implications for decision-makers, revolutionizing their comprehension of organizational culture. Tackling the challenge of mapping the digital organization journey involves innovative methodologies that probe not only external landscapes but also internal cultural dynamics. This holistic approach furnishes decision-makers with a nuanced understanding of their organizational culture and visualizes pivotal skills for employee growth. This clarity enables informed choices resonating with the organization's unique cultural fabric. Anticipated outcomes transcend mere individual cultural measurements, aligning with organizational goals to unveil a comprehensive view of culture, exposing artifacts and depth. Armed with this profound understanding, decision-makers gain tangible evidence for informed decision-making, strategically leveraging cultural strengths to cultivate an environment conducive to growth, innovation, and enduring success, ultimately leading to measurable outcomes.

Keywords: leadership, cooperation, collaboration, teamwork, work culture

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Authors: Dimitra C. Banti, Gesthimani Liona, Petros Samaras, Manasis Mitrakas

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Municipal and industrial wastewaters are often treated biologically, by the activated sludge process (ASP). The ASP not only requires large aeration and sedimentation tanks, but also generates large quantities of excess sludge. An alternative technology is the membrane bioreactor (MBR), which replaces two stages of the conventional ASP—clarification and settlement—with a single, integrated biotreatment and clarification step. The advantages offered by the MBR over conventional treatment include reduced footprint and sludge production through maintaining a high biomass concentration in the bioreactor. Notwithstanding these advantages, the widespread application of the MBR process is constrained by membrane fouling. Fouling leads to permeate flux decline, making more frequent membrane cleaning and replacement necessary and resulting to increased operating costs. In general, membrane fouling results from the interaction between the membrane material and the components in the activated sludge liquor. The latter includes substrate components, cells, cell debris and microbial metabolites, such as Extracellular Polymeric Substances (EPS) and Sludge Microbial Products (SMPs). The challenge for effective MBR operation is to minimize the rate of Transmembrane Pressure (TMP) increase. This can be achieved by several ways, one of which is the addition of specific additives, that enhance the coagulation and flocculation of compounds, which are responsible for fouling, hence reducing biofilm formation on the membrane surface and limiting the fouling rate. In this project the effectiveness of a non-commercial composite coagulant was studied as an agent for fouling control in a lab scale MBR system consisting in two aerated tanks. A flat sheet membrane module with 0.40 um pore size was submerged into the second tank. The system was fed by50 L/d of municipal wastewater collected from the effluent of the primary sedimentation basin. The TMP increase rate, which is directly related to fouling growth, was monitored by a PLC system. EPS, MLSS and MLVSS measurements were performed in samples of mixed liquor; in addition, influent and effluent samples were collected for the determination of physicochemical characteristics (COD, BOD5, NO3-N, NH4-N, Total N and PO4-P). The coagulant was added in concentrations 2, 5 and 10mg/L during a period of 2 weeks and the results were compared with the control system (without coagulant addition). EPS fractions were extracted by a three stages physical-thermal treatment allowing the identification of Soluble EPS (SEPS) or SMP, Loosely Bound EPS (LBEPS) and Tightly Bound EPS (TBEPS). Proteins and carbohydrates concentrations were measured in EPS fractions by the modified Lowry method and Dubois method, respectively. Addition of 2 mg/L coagulant concentration did not affect SEPS proteins in comparison with control process and their values varied between 32 to 38mg/g VSS. However a coagulant dosage of 5mg/L resulted in a slight increase of SEPS proteins at 35-40 mg/g VSS while 10mg/L coagulant further increased SEPS to 44-48mg/g VSS. Similar results were obtained for SEPS carbohydrates. Carbohydrates values without coagulant addition were similar to the corresponding values measured for 2mg/L coagulant; the addition of mg/L coagulant resulted to a slight increase of carbohydrates SEPS to 6-7mg/g VSS while a dose of 10 mg/L further increased carbohydrates content to 9-10mg/g VSS. Total LBEPS and TBEPS, consisted of proteins and carbohydrates of LBEPS and TBEPS respectively, presented similar variations by the addition of the coagulant. Total LBEPS at 2mg/L dose were almost equal to 17mg/g VSS, and their values increased to 22 and 29 mg/g VSS during the addition of 5 mg/L and 10 mg/L of coagulant respectively. Total TBEPS were almost 37 mg/g VSS at a coagulant dose of 2 mg/L and increased to 42 and 51 mg/g VSS at 5 mg/L and 10 mg/L doses, respectively. Therefore, it can be concluded that coagulant addition could potentially affect microorganisms activities, excreting EPS in greater amounts. Nevertheless, EPS increase, mainly SEPS increase, resulted to a higher membrane fouling rate, as justified by the corresponding TMP increase rate. However, the addition of the coagulant, although affected the EPS content in the reactor mixed liquor, did not change the filtration process: an effluent of high quality was produced, with COD values as low as 20-30 mg/L.

Keywords: extracellular polymeric substances, MBR, membrane fouling, EPS

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Authors: Davide Palma, Dimitra Papagiannaki, Marco Minella, Manuel Lai, Rita Binetti, Claire Richard

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Modern analytical technologies allow us to detect water contaminants at trace and ultra-trace concentrations highlighting how a large number of organic compounds is not efficiently abated by most wastewater treatment facilities relying on biological processes; we usually refer to these micropollutants as contaminants of emerging concern (CECs). The availability of reliable end effective technologies, able to guarantee the high standards of water quality demanded by legislators worldwide, has therefore become a primary need. In this context, water plasma stands out among developing technologies as it is extremely effective in the abatement of numerous classes of pollutants, cost-effective, and environmentally friendly. In this work, a custom-built non-thermal pulsed plasma discharge generator was used to abate the concentration of selected CECs in the water samples. Samples were treated in a 50 mL pyrex reactor using two different types of plasma discharge occurring at the surface of the treated solution or, underwater, working with positive polarity. The distance between the tips of the electrodes determined where the discharge was formed: underwater when the distance was < 2mm, at the water surface when the distance was > 2 mm. Peak voltage was in the 100-130kV range with typical current values of 20-40 A. The duration of the pulse was 500 ns, and the frequency of discharge could be manually set between 5 and 45 Hz. Treatment of 100 µM diclofenac solution in MilliQ water, with a pulse frequency of 17Hz, revealed that surface discharge was more efficient in the degradation of diclofenac that was no longer detectable after 6 minutes of treatment. Over 30 minutes were required to obtain the same results with underwater discharge. These results are justified by the higher rate of H₂O₂ formation (21.80 µmolL⁻¹min⁻¹ for surface discharge against 1.20 µmolL⁻¹min⁻¹ for underwater discharge), larger discharge volume and UV light emission, high rate of ozone and NOx production (up to 800 and 1400 ppb respectively) observed when working with surface discharge. Then, the surface discharge was used for the treatment of the three selected perfluoroalkyl compounds, namely, perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA), and pefluorooctanesulfonic acid (PFOS) both individually and in mixture, in ultrapure and groundwater matrices with initial concentration of 1 ppb. In both matrices, PFOS exhibited the best degradation reaching complete removal after 30 min of treatment (degradation rate 0.107 min⁻¹ in ultrapure water and 0.0633 min⁻¹ in groundwater), while the degradation rate of PFOA and PFHxA was slower of around 65% and 80%, respectively. Total nitrogen (TN) measurements revealed levels up to 45 mgL⁻¹h⁻¹ in water samples treated with surface discharge, while, in analogous samples treated with underwater discharge, TN increase was 5 to 10 times lower. These results can be explained by the significant NOx concentrations (over 1400 ppb) measured above functioning reactor operating with superficial discharge; rapid NOx hydrolysis led to nitrates accumulation in the solution explaining the observed evolution of TN values. Ionic chromatography measures confirmed that the vast majority of TN was under the form of nitrates. In conclusion, non-thermal pulsed plasma discharge, obtained with a custom-built generator, was proven to effectively degrade diclofenac in water matrices confirming the potential interest of this technology for wastewater treatment. The surface discharge was proven to be more effective in CECs removal due to the high rate of formation of H₂O₂, ozone, reactive radical species, and strong UV light emission. Furthermore, nitrates enriched water obtained after treatment could be an interesting added-value product to be used as fertilizer in agriculture. Acknowledgment: This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 765860.

Keywords: CECs removal, nitrogen fixation, non-thermal plasma, water treatment

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

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

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

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Authors: P. J. Sweeney, T. Ahtoniemi, J. Puoliväli, T. Laitinen, K.Lehtimäki, A. Nurmi, D. Wells

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Duchenne muscular dystrophy (DMD) is an X-linked, lethal muscle wasting disease for which there are currently no treatment that effectively prevents the muscle necrosis and progressive muscle loss. DMD is among the most common of inherited diseases affecting around 1/3500 live male births. MDX (X-linked muscular dystrophy) mice only partially encapsulate the disease in humans and display weakness in muscles, muscle damage and edema during a period deemed the “critical period” when these mice go through cycles of muscular degeneration and regeneration. Although the MDX mutant mouse model has been extensively studied as a model for DMD, to-date an extensive temporal, non-invasive imaging profile that utilizes magnetic resonance imaging (MRI) and 1H-magnetic resonance spectroscopy (1H-MRS) has not been performed.. In addition, longitudinal imaging characterization has not coincided with attempts to exacerbate the progressive muscle damage by exercise. In this study we employed an 11.7 T small animal MRI in order to characterize the MRI and MRS profile of MDX mice longitudinally during a 12 month period during which MDX mice were subjected to exercise. Male mutant MDX mice (n=15) and male wild-type mice (n=15) were subjected to a chronic exercise regime of treadmill walking (30 min/ session) bi-weekly over the whole 12 month follow-up period. Mouse gastrocnemius and tibialis anterior muscles were profiled with baseline T2-MRI and 1H-MRS at 6 weeks of age. Imaging and spectroscopy was repeated again at 3 months, 6 months, 9 months and 12 months of age. Plasma creatine kinase (CK) level measurements were coincided with time-points for T2-MRI and 1H-MRS, but also after the “critical period” at 10 weeks of age. The results obtained from this study indicate that chronic exercise extends dystrophic phenotype of MDX mice as evidenced by T2-MRI and1H-MRS. T2-MRI revealed extent and location of the muscle damage in gastrocnemius and tibialis anterior muscles as hyperintensities (lesions and edema) in exercised MDX mice over follow-up period.. The magnitude of the muscle damage remained stable over time in exercised mice. No evident fat infiltration or cumulation to the muscle tissues was seen at any time-point in exercised MDX mice. Creatine, choline and taurine levels evaluated by 1H-MRS from the same muscles were found significantly decreased in each time-point, Extramyocellular (EMCL) and intramyocellular lipids (IMCL) did not change in exercised mice supporting the findings from anatomical T2-MRI scans for fat content. Creatine kinase levels were found to be significantly higher in exercised MDX mice during the follow-up period and importantly CK levels remained stable over the whole follow-up period. Taken together, we have described here longitudinal prophile for muscle damage and muscle metabolic changes in MDX mice subjected to chronic exercised. The extent of the muscle damage by T2-MRI was found to be stable through the follow-up period in muscles examined. In addition, metabolic profile, especially creatine, choline and taurine levels in muscles, was found to be sustained between time-points. The anatomical muscle damage evaluated by T2-MRI was supported by plasma CK levels which remained stable over the follow-up period. These findings show that non-invasive imaging and spectroscopy can be used effectively to evaluate chronic muscle pathology. These techniques can be also used to evaluate the effect of various manipulations, like here exercise, on the phenotype of the mice. Many of the findings we present here are translatable to clinical disease, such as decreased creatine, choline and taurine levels in muscles. Imaging by T2-MRI and 1H-MRS also revealed that fat content or extramyocellar and intramyocellular lipids, respectively, are not changed in MDX mice, which is in contrast to clinical manifestation of the Duchenne’s muscle dystrophy. Findings show that non-invasive imaging can be used to characterize the phenotype of a MDX model and its translatability to clinical disease, and to study events that have traditionally been not examined, like here rigorous exercise related sustained muscle damage after the “critical period”. The ability for this model to display sustained damage beyond the spontaneous “critical period“ and in turn to study drug effects on this extended phenotype will increase the value of the MDX mouse model as a tool to study therapies and treatments aimed at DMD and associated diseases.

Keywords: 1H-MRS, MRI, muscular dystrophy, mouse model

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Authors: M. Moreno, M. Alique, D. Otero, C. Delgado, P. Lacharmoise, L. Gracia, L. Pires, A. Moya

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Marine environments are increasingly threatened by heavy metal contamination, including mercury (Hg), lead (Pb), and cadmium (Cd), posing significant risks to ecosystems and human health. Traditional monitoring techniques often fail to provide the spatial and temporal resolution needed for real-time detection of these contaminants, especially in remote or harsh environments. SEAWIZARD addresses these challenges by leveraging the flexibility, adaptability, and cost-effectiveness of printed electronics, with the integration of microfluidics to develop a compact, portable, and reusable sensor platform designed specifically for real-time monitoring of heavy metal ions in seawater. The SEAWIZARD sensor is a multiparametric Lab-on-Chip (LoC) device, a miniaturized system that integrates several laboratory functions into a single chip, drastically reducing sample volumes and improving adaptability. This platform integrates three printed graphene electrodes for the simultaneous detection of Hg, Cd and Pb via square wave voltammetry. These electrodes share the reference and the counter electrodes to improve space efficiency. Additionally, it integrates printed pH and temperature sensors to correct environmental interferences that may impact the accuracy of metal detection. The pH sensor is based on a carbon electrode with iridium oxide electrodeposited while the temperature sensor is graphene based. A protective dielectric layer is printed on top of the sensor to safeguard it in harsh marine conditions. The use of flexible polyethylene terephthalate (PET) as the substrate enables the sensor to conform to various surfaces and operate in challenging environments. One of the key innovations of SEAWIZARD is its integrated microfluidic layer, fabricated from cyclic olefin copolymer (COC). This microfluidic component allows a controlled flow of seawater over the sensing area, allowing for significant improved detection limits compared to direct water sampling. The system’s dual-channel design separates the detection of heavy metals from the measurement of pH and temperature, ensuring that each parameter is measured under optimal conditions. In addition, the temperature sensor is finely tuned with a serpentine-shaped microfluidic channel to ensure precise thermal measurements. SEAWIZARD also incorporates custom electronics that allow for wireless data transmission via Bluetooth, facilitating rapid data collection and user interface integration. Embedded artificial intelligence further enhances the platform by providing an automated alarm system, capable of detecting predefined metal concentration thresholds and issuing warnings when limits are exceeded. This predictive feature enables early warnings of potential environmental disasters, such as industrial spills or toxic levels of heavy metal pollutants, making SEAWIZARD not just a detection tool, but a comprehensive monitoring and early intervention system. In conclusion, SEAWIZARD represents a significant advancement in printed electronics applied to environmental sensing. By combining flexible, low-cost materials with advanced microfluidics, custom electronics, and AI-driven intelligence, SEAWIZARD offers a highly adaptable and scalable solution for real-time, high-resolution monitoring of heavy metals in marine environments. Its compact and portable design makes it an accessible, user-friendly tool with the potential to transform water quality monitoring practices and provide critical data to protect marine ecosystems from contamination-related risks.

Keywords: lab-on-chip, printed electronics, real-time monitoring, microfluidics, heavy metal contamination

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Authors: Istvan Csarnovics, Attila Bonyar, Miklos Veres, Laszlo Himics, Attila Csik, Judit Kaman, Julia Burunkova, Geza Szanto, Laszlo Balazs, Sandor Kokenyesi

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In this work, the performance of gold nanoparticles were investigated for stimulation of photosensitive materials for photonic applications. It was widely used for surface plasmon resonance experiments, not in the last place because of the manifestation of optical resonances in the visible spectral region. The localized surface plasmon resonance is rather easily observed in nanometer-sized metallic structures and widely used for measurements, sensing, in semiconductor devices and even in optical data storage. Firstly, gold nanoparticles on silica glass substrate satisfy the conditions for surface plasmon resonance in the green-red spectral range, where the chalcogenide glasses have the highest sensitivity. The gold nanostructures influence and enhance the optical, structural and volume changes and promote the exciton generation in gold nanoparticles/chalcogenide layer structure. The experimental results support the importance of localized electric fields in the photo-induced transformation of chalcogenide glasses as well as suggest new approaches to improve the performance of these optical recording media. Results may be utilized for direct, micrometre- or submicron size geometrical and optical pattern formation and used also for further development of the explanations of these effects in chalcogenide glasses. Besides of that, gold nanoparticles could be added to the organic light-sensitive material. The acrylate-based materials are frequently used for optical, holographic recording of optoelectronic elements due to photo-stimulated structural transformations. The holographic recording process and photo-polymerization effect could be enhanced by the localized plasmon field of the created gold nanostructures. Finally, gold nanoparticles widely used for electrochemical and optical sensor applications. Although these NPs can be synthesized in several ways, perhaps one of the simplest methods is the thermal annealing of pre-deposited thin films on glass or silicon surfaces. With this method, the parameters of the annealing process (time, temperature) and the pre-deposited thin film thickness influence and define the resulting size and distribution of the NPs on the surface. Localized surface plasmon resonance (LSPR) is a very sensitive optical phenomenon and can be utilized for a large variety of sensing purposes (chemical sensors, gas sensors, biosensors, etc.). Surface-enhanced Raman spectroscopy (SERS) is an analytical method which can significantly increase the yield of Raman scattering of target molecules adsorbed on the surface of metallic nanoparticles. The sensitivity of LSPR and SERS based devices is strongly depending on the used material and also on the size and geometry of the metallic nanoparticles. By controlling these parameters the plasmon absorption band can be tuned and the sensitivity can be optimized. The technological parameters of the generated gold nanoparticles were investigated and influence on the SERS and on the LSPR sensitivity was established. The LSPR sensitivity were simulated for gold nanocubes and nanospheres with MNPBEM Matlab toolbox. It was found that the enhancement factor (which characterize the increase in the peak shift for multi-particle arrangements compared to single-particle models) depends on the size of the nanoparticles and on the distance between the particles. This work was supported by GINOP- 2.3.2-15-2016-00041 project, which is co-financed by the European Union and European Social Fund. Istvan Csarnovics is grateful for the support through the New National Excellence Program of the Ministry of Human Capacities, supported by the ÚNKP-17-4 Attila Bonyár and Miklós Veres are grateful for the support of the János Bolyai Research Scholarship of the Hungarian Academy of Sciences.

Keywords: light sensitive nanocomposites, metallic nanoparticles, photonic application, plasmonic nanostructures

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Authors: Katerina Zaharieva, Katya Milenova, Zara Cherkezova-Zheleva, Alexander Eliyas, Boris Kunev, Ivan Mitov

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The synthesized nanosized manganese ferrite-type of samples have been tested as photocatalysts in the reaction of oxidative degradation of model contaminant Reactive Black 5 (RB5) dye in aqueous solutions under UV irradiation. As it is known this azo dye is applied in the textile-coloring industry and it is discharged into the waterways causing pollution. The co-precipitation procedure has been used for the synthesis of manganese ferrite-type of materials: Sample 1 - Mn0.25Fe2.75O4, Sample 2 - Mn0.5Fe2.5O4 and Sample 3 - MnFe2O4 from 0.03M aqueous solutions of MnCl2•4H2O, FeCl2•4H2O and/or FeCl3•6H2O and 0.3M NaOH in appropriate amounts. The mechanochemical activation of co-precipitated ferrite-type of samples has been performed in argon (Samples 1 and 2) or in air atmosphere (Sample 3) for 2 hours at a milling speed of 500 rpm. The mechano-chemical treatment has been carried out in a high energy planetary ball mill type PM 100, Retsch, Germany. The mass ratio between balls and powder was 30:1. As a result mechanochemically activated Sample 4 - Mn0.25Fe2.75O4, Sample 5 - Mn0.5Fe2.5O4 and Sample 6 - MnFe2O4 have been obtained. The synthesized manganese ferrite-type photocatalysts have been characterized by X-ray diffraction method and Moessbauer spectroscopy. The registered X-ray diffraction patterns and Moessbauer spectra of co-precipitated ferrite-type of materials show the presence of manganese ferrite and additional akaganeite phase. The presence of manganese ferrite and small amounts of iron phases is established in the mechanochemically treated samples. The calculated average crystallite size of manganese ferrites varies within the range 7 – 13 nm. This result is confirmed by Moessbauer study. The registered spectra show superparamagnetic behavior of the prepared materials at room temperature. The photocatalytic investigations have been made using polychromatic UV-A light lamp (Sylvania BLB, 18 W) illumination with wavelength maximum at 365 nm. The intensity of light irradiation upon the manganese ferrite-type photocatalysts was 0.66 mW.cm-2. The photocatalytic reaction of oxidative degradation of RB5 dye was carried out in a semi-batch slurry photocatalytic reactor with 0.15 g of ferrite-type powder, 150 ml of 20 ppm dye aqueous solution under magnetic stirring at rate 400 rpm and continuously feeding air flow. The samples achieved adsorption-desorption equilibrium in the dark period for 30 min and then the UV-light was turned on. After regular time intervals aliquot parts from the suspension were taken out and centrifuged to separate the powder from solution. The residual concentrations of dye were established by a UV-Vis absorbance single beam spectrophotometer CamSpec M501 (UK) measuring in the wavelength region from 190 to 800 nm. The photocatalytic measurements determined that the apparent pseudo-first-order rate constants calculated by linear slopes approximating to first order kinetic equation, increase in following order: Sample 3 (1.1х10-3 min-1) < Sample 1 (2.2х10-3 min-1) < Sample 2 (3.3 х10-3 min-1) < Sample 4 (3.8х10-3 min-1) < Sample 6 (11х10-3 min-1) < Sample 5 (15.2х10-3 min-1). The mechanochemically activated manganese ferrite-type of photocatalyst samples show significantly higher degree of oxidative degradation of RB5 dye after 120 minutes of UV light illumination in comparison with co-precipitated ferrite-type samples: Sample 5 (92%) > Sample 6 (91%) > Sample 4 (63%) > Sample 2 (53%) > Sample 1 (42%) > Sample 3 (15%). Summarizing the obtained results we conclude that the mechanochemical activation leads to a significant enhancement of the degree of oxidative degradation of the RB5 dye and photocatalytic activity of tested manganese ferrite-type of catalyst samples under our experimental conditions. The mechanochemically activated Mn0.5Fe2.5O4 ferrite-type of material displays the highest photocatalytic activity (15.2х10-3 min-1) and degree of oxidative degradation of the RB5 dye (92%) compared to the other synthesized samples. Especially a significant improvement in the degree of oxidative degradation of RB5 dye (91%) has been determined for mechanochemically treated MnFe2O4 ferrite-type of sample with the highest extent of substitution of iron ions by manganese ions than in the case of the co-precipitated MnFe2O4 sample (15%). The mechanochemically activated manganese ferrite-type of samples show good photocatalytic properties in the reaction of oxidative degradation of RB5 azo dye in aqueous solutions and it could find potential application for dye removal from wastewaters originating from textile industry.

Keywords: nanostructured manganese ferrite-type materials, photocatalytic activity, Reactive Black 5, water treatment

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