Search results for: bulk

Authors: S. E. Mohmad-Saberi, W. Song, N. Oliver, M. Adrian, T.C. Hsu, A. Darbyshire

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Biodegradable polyurethane (PU) has emerged as a potential material to promote repair and regeneration of damaged/diseased tissues in heart valve regeneration due to its excellent biomechanical profile. Understanding the effects of sterilization on their properties is vital since they are more sensitive and more critical of porous structures compared to bulk ones. In this study, the effects of low concentration of hydrogen peroxide (H₂O₂) solution sterilization has been investigated to determine whether the procedure would be efficient and non-destructive to porous three-dimensional (3D) elastomeric nanocomposite, polyhedral oligomeric silsesquioxane-terminated poly (ethylene-diethylene glycol succinate-sebacate) urea-urethane (POSS-EDSS-PU) scaffold. All the samples were tested for sterility following sterilization using phosphate buffer saline (PBS) as control and 5 % v/v H₂O₂ solution. The samples were incubated in tryptic soy broth for the cultivation of microorganisms under agitation at 37˚C for 72 hours. The effects of the 5 % v/v H₂O₂ solution sterilization were evaluated in terms of morphology, chemical and mechanical properties using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and tensile tester apparatus. Toxicity effects of the 5 % v/v H₂O₂ solution decontamination were studied by in vitro cytotoxicity test, where the cellular responses of human dermal fibroblast (HDF) were examined. A clear, uncontaminated broth using 5 % v/v H₂O₂ solution method indicated efficient sterilization after 3 days, while the non-sterilized control shows clouding broth indicated contamination. The morphology of 3D POSS-EDSS-PU scaffold appeared to have similar morphology after sterilization with 5 % v/v H₂O₂ solution regarding of pore size and surface. FTIR results show that the sterilized samples and non-sterilized control share the same spectra pattern, confirming no significant alterations over the surface chemistry. For the mechanical properties of the H₂O₂ solution-treated scaffolds, the tensile strain was not significantly decreased, however, become significantly stiffer after the sterilization. No cytotoxic effects were observed after the 5 % v/v H₂O₂ solution sterilization as confirmed by cell viability assessed by Alamar Blue assay. The results suggest that low concentration of 5 % v/v hydrogen peroxide solution can be used as an alternative method for sterilizing biodegradable 3D porous scaffold with micro/nano-architecture without structural deformation. This study provides the understanding of the sterilization effects on biomechanical profile and cell proliferation of 3D POSS-EDSS-PU scaffolds.

Keywords: biodegradable, hydrogen peroxide solution, POSS-EDSS-PU, sterilization

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Authors: A. T. Perez Fontenla, S. Sgobba, A. Bartkowska, Y. Askar, M. Dalemir Celuch, A. Newborough, M. Karppinen, H. Haalien, S. Deleval, S. Larcher, C. Charvet, L. Bruno, R. Trant

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The present study investigates the corrosion behavior of copper (Cu) based conducts predominantly brazed with Sil-Fos (self-fluxing copper-based filler with silver and phosphorus) within various cooling circuits of demineralized water across different particle accelerator components at CERN. The study covers a range of sample service time, from a few months to fifty years, and includes various accelerator components such as quadrupoles, dipoles, and bending magnets. The investigation comprises the established sample extraction procedure, examination methodology including non-destructive testing, evaluation of the corrosion phenomena, and identification of commonalities across the studied components as well as analysis of the environmental influence. The systematic analysis included computed microtomography (CT) of the joints that revealed distributed defects across all brazing interfaces. Some defects appeared to result from areas not wetted by the filler during the brazing operation, displaying round shapes, while others exhibited irregular contours and radial alignment, indicative of a network or interconnection. The subsequent dry cutting performed facilitated access to the conduct's inner surface and the brazed joints for further inspection through light and electron microscopy (SEM) and chemical analysis via Energy Dispersive X-ray spectroscopy (EDS). Brazing analysis away from affected areas identified the expected phases for a Sil-Fos alloy. In contrast, the affected locations displayed micrometric cavities propagating into the material, along with selective corrosion of the bulk Cu initiated at the conductor-braze interface. Corrosion product analysis highlighted the consistent presence of sulfur (up to 6 % in weight), whose origin and role in the corrosion initiation and extension is being further investigated. The importance of this study is paramount as it plays a crucial role in comprehending the underlying factors contributing to recently identified water leaks and evaluating the extent of the issue. Its primary objective is to provide essential insights for the repair of impacted brazed joints when accessibility permits. Moreover, the study seeks to contribute to the improvement of design and manufacturing practices for future components, ultimately enhancing the overall reliability and performance of magnet systems within CERN accelerator facilities.

Keywords: accelerator facilities, brazed copper conducts, demineralized water, magnets

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Authors: A. Hamza, H. Kathyayini, N. Nagaraju

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Aluminophosphates, both amorphous and crystalline materials find applications as adsorbents, ceramics, and pigments and as catalysts/catalyst supports in organic fine chemical synthesis. Most of the applications are varied depending on the type of metal incorporated, particle size, surface area, porosity and morphology of aluminophosphate. The porous and surface properties of these materials are normally fine-tuned by adopting various preparation methodologies. Numerous crystalline microporous and mesoporous aluminophosphates and metal-aluminophosphates have been reported in literature, in which the synthesis has been carried out by using structure directing organic molecules/surfactants. In present work, amorphous aluminophosphate (AlP) and metal-aluminophosphates MAlP (M = Cu, Zn, Cr, Fe, Ce and Zr) and their mixed forms M-1M2AlP are prepared under a typical precipitation condition, i.e. at low temperature in order to keep the Von-Weirmann relative super saturation of the precipitating medium and obtain small size precipitate particles. These materials are prepared without using any surfactants. All materials are thoroughly characterised for surface and bulk properties by N2 adsorption-desorption technique, XRD, FT-IR, TG and SEM. The materials are also analysed for the amount and the strength of their surface acid sites, by NH3-TPD and CO2-TPD techniques respectively. All the materials prepared in the work are investigated for their catalytic activity in following applications in the synthesis of industrially important Jasminaldehyde via, aldol condensation of n-heptanal and benzaldehyde, in the synthesis of biologically important chalcones by Claisen-shmidth condensation of benzaldehyde and substituted chalcones. The effect of the amount of the catalysts, duration of the reaction, temperature of the reaction, molar ratio of the reactants has been studied. The porosity of pure aluminophosphate is found to be changed significantly by the incorporation of transition metals during preparation of aluminophosphate. The pore size increased from microporous to mesoporous and finally to macroporous by following order of metals Cu = Zn < Cr < Ce < Fe = Zr. The change in surface area and porosity of double metal-aluminophosphates depended on the concentration of both the metals. The acidity of aluminophosphate is either increased or decreased which depended on the type and valence of metals loaded. A good number of basic sites are created in metal-aluminophosphates irrespective of the metals used. A maximum catalytic activity for synthesis of both jasminaldehyde and chalcone is obtained by FeAlP as catalysts; these materials are characterized by decreased strength and concentration of acidic sites with optimum level basic sites.

Keywords: amorphous metal-aluminophosphates, surface properties, acidic-basic properties, Aldol, Claisen-Shmidth condensation, jasminaldehyde, chalcone

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Authors: Benjamin Blat Belmonte, Stephan Rinderknecht

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The transition to electric vehicles (EVs) stands at the forefront of innovative strategies designed to address environmental concerns and reduce fossil fuel dependency. As the number of EVs on the roads increases, so too does the potential for their integration into energy markets. This research dives deep into the transformative possibilities of using electric vehicle fleets, specifically electric bus fleets, not just as consumers but as active participants in the energy market. This paper investigates the feasibility and grid effects of electric vehicle fleet operators in the energy market. Our objective centers around a comprehensive exploration of the sector coupling domain, with an emphasis on the economic potential in both electricity and balancing markets. Methodologically, our approach combines data mining techniques with thorough pre-processing, pulling from a rich repository of electricity and balancing market data. Our findings are grounded in the actual operational realities of the bus fleet operator in Darmstadt, Germany. We employ a Mixed Integer Linear Programming (MILP) approach, with the bulk of the computations being processed on the High-Performance Computing (HPC) platform ‘Lichtenbergcluster’. Our findings underscore the compelling economic potential of EV fleets in the energy market. With electric buses becoming more prevalent, the considerable size of these fleets, paired with their substantial battery capacity, opens up new horizons for energy market participation. Notably, our research reveals that economic viability is not the sole advantage. Participating actively in the energy market also translates into pronounced positive effects on grid stabilization. Essentially, EV fleet operators can serve a dual purpose: facilitating transport while simultaneously playing an instrumental role in enhancing grid reliability and resilience. This research highlights the symbiotic relationship between the growth of EV fleets and the stabilization of the energy grid. Such systems could lead to both commercial and ecological advantages, reinforcing the value of electric bus fleets in the broader landscape of sustainable energy solutions. In conclusion, the electrification of transport offers more than just a means to reduce local greenhouse gas emissions. By positioning electric vehicle fleet operators as active participants in the energy market, there lies a powerful opportunity to drive forward the energy transition. This study serves as a testament to the synergistic potential of EV fleets in bolstering both economic viability and grid stabilization, signaling a promising trajectory for future sector coupling endeavors.

Keywords: electric vehicle fleet, sector coupling, optimization, electricity market, balancing market

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Authors: Ali Abdul Kadhim, Fue Lien

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Solid particle distribution on an impingement surface has been simulated utilizing a graphical processing unit (GPU). In-house computational fluid dynamics (CFD) code has been developed to investigate a 3D turbulent impinging jet using the lattice Boltzmann method (LBM) in conjunction with large eddy simulation (LES) and the multiple relaxation time (MRT) models. This paper proposed an improvement in the LBM-cellular automata (LBM-CA) probabilistic method. In the current model, the fluid flow utilizes the D3Q19 lattice, while the particle model employs the D3Q27 lattice. The particle numbers are defined at the same regular LBM nodes, and transport of particles from one node to its neighboring nodes are determined in accordance with the particle bulk density and velocity by considering all the external forces. The previous models distribute particles at each time step without considering the local velocity and the number of particles at each node. The present model overcomes the deficiencies of the previous LBM-CA models and, therefore, can better capture the dynamic interaction between particles and the surrounding turbulent flow field. Despite the increasing popularity of LBM-MRT-CA model in simulating complex multiphase fluid flows, this approach is still expensive in term of memory size and computational time required to perform 3D simulations. To improve the throughput of each simulation, a single GeForce GTX TITAN X GPU is used in the present work. The CUDA parallel programming platform and the CuRAND library are utilized to form an efficient LBM-CA algorithm. The methodology was first validated against a benchmark test case involving particle deposition on a square cylinder confined in a duct. The flow was unsteady and laminar at Re=200 (Re is the Reynolds number), and simulations were conducted for different Stokes numbers. The present LBM solutions agree well with other results available in the open literature. The GPU code was then used to simulate the particle transport and deposition in a turbulent impinging jet at Re=10,000. The simulations were conducted for L/D=2,4 and 6, where L is the nozzle-to-surface distance and D is the jet diameter. The effect of changing the Stokes number on the particle deposition profile was studied at different L/D ratios. For comparative studies, another in-house serial CPU code was also developed, coupling LBM with the classical Lagrangian particle dispersion model. Agreement between results obtained with LBM-CA and LBM-Lagrangian models and the experimental data is generally good. The present GPU approach achieves a speedup ratio of about 350 against the serial code running on a single CPU.

Keywords: CUDA, GPU parallel programming, LES, lattice Boltzmann method, MRT, multi-phase flow, probabilistic model

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Authors: Karolina Ordon, Sandrine Coste, Malgorzata Makowska-Janusik, Abdelhadi Kassiba

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Photocatalytic processes play key role in the production of a new source of energy (as hydrogen), design of self-cleaning surfaces or for the environment preservation. The most challenging task deals with the purification of water distinguished by high efficiency. In the mentioned process, organic pollutants in solutions are decomposed to the simple, non-toxic compounds as H2O and CO2. The most known photocatalytic materials are ZnO, CdS and TiO2 semiconductors with a particular involvement of TiO2 as an efficient photocatalysts even with a high band gap equal to 3.2 eV which exploit only UV radiation from solar emitted spectrum. However, promising material with visible light induced photoactivity was searched through the monoclinic polytype of BiVO4 which has energy gap about 2.4 eV. As required in heterogeneous photocatalysis, the high contact surface is required. Also, BiVO4 as photocatalyst can be optimized by increasing its surface area by achieving the mesoporous structure synthesize. The main goal of the present work consists in the synthesis and characterization of BiVO4 mesoporous thin film. The synthesis method based on sol-gel was carried out using a standard surfactants such as P123 and F127. The thin film was deposited by spin and dip coating method. Then, the structural analysis of the obtained material was performed thanks to X-ray diffraction (XRD) and Raman spectroscopy. The surface of resulting structure was investigated using a scanning electron microscopy (SEM). The computer simulations based on modeling the optical and electronic properties of bulk BiVO4 by using DFT (density functional theory) methodology were carried out. The semiempirical parameterized method PM6 was used to compute the physical properties of BiVO4 nanostructures. The Raman and IR absorption spectra were also measured for synthesized mesoporous material, and the results were compared with the theoretical predictions. The simulations of nanostructured BiVO4 have pointed out the occurrence of quantum confinement for nanosized clusters leading to widening of the band gap. This result overcame the relevance of nanosized objects to harvest wide part of the solar spectrum. Also, a balance was searched experimentally through the mesoporous nature of the films devoted to enhancing the contact surface as required for heterogeneous catalysis without to lower the nanocrystallite size under some critical sizes inducing an increased band gap. The present contribution will discuss the relevant features of the mesoporous films with respect to their photocatalytic responses.

Keywords: bismuth vanadate, photocatalysis, thin film, quantum-chemical calculations

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Authors: Cécile Dufloux, Klaus Böttcher, Heike Oppermann, Jürgen Wollweber

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Hexagonal aluminum nitride (AlN) is a promising candidate for several wide band gap semiconductor compound applications such as deep UV light emitting diodes (UVC LED) and fast power transistors (HEMTs). To date, bulk AlN single crystals are still commonly grown from the physical vapor transport (PVT). Single crystalline AlN wafers obtained from this process could offer suitable substrates for a defect-free growth of ultimately active AlGaN layers, however, these wafers still lack from small sizes, limited delivery quantities and high prices so far.Although there is already an increasing interest in the commercial availability of AlN wafers, comparatively cheap Si, SiC or sapphire are still predominantly used as substrate material for the deposition of active AlGaN layers. Nevertheless, due to a lattice mismatch up to 20%, the obtained material shows high defect densities and is, therefore, less suitable for high power devices as described above. Therefore, the use of AlN with specially adapted properties for optical and sensor applications could be promising for mass market products which seem to fulfill fewer requirements. To respond to the demand of suitable AlN target material for the growth of AlGaN layers, we have designed an innovative technology based on reactive plasma spraying. The goal is to produce coarse grained AlN boules with N-terminated columnar structure and high purity. In this process, aluminum is injected into a microwave stimulated nitrogen plasma. AlN, as the product of the reaction between aluminum powder and the plasma activated N2, is deposited onto the target. We used an aluminum filament as the initial material to minimize oxygen contamination during the process. The material was guided through the nitrogen plasma so that the mass turnover was 10g/h. To avoid any impurity contamination by an erosion of the electrodes, an electrode-less discharge was used for the plasma ignition. The pressure was maintained at 600-700 mbar, so the plasma reached a temperature high enough to vaporize the aluminum which subsequently was reacting with the surrounding plasma. The obtained products consist of thick polycrystalline AlN layers with a diameter of 2-3 cm. The crystallinity was determined by X-ray crystallography. The grain structure was systematically investigated by optical and scanning electron microscopy. Furthermore, we performed a Raman spectroscopy to provide evidence of stress in the layers. This paper will discuss the effects of process parameters such as microwave power and deposition geometry (specimen holder, radiation shields, ...) on the topography, crystallinity, and stress distribution of AlN.

Keywords: aluminum nitride, polycrystal, reactive plasma spraying, semiconductor

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Authors: Farhina Haque, Chanyeop Park

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The high efficiency, high field, and high power density provided by wide bandgap (WBG) semiconductors and advanced power electronic converter (PEC) topologies enabled the dynamic control of power in medium to high voltage systems. Although WBG semiconductors outperform the conventional Silicon based devices in terms of voltage rating, switching speed, and efficiency, the increased voltage handling properties, high dv/dt, and compact device packaging increase local electric fields, which are the main causes of partial discharge (PD) in the advanced medium and high voltage applications. PD, which occurs actively in voids, triple points, and airgaps, is an inevitable dielectric challenge that causes insulation and device aging. The aging process accelerates over time and eventually leads to the complete failure of the applications. Hence, it is critical to mitigating PD. Sharp edges, airgaps, triple points, and bubbles are common defects that exist in any medium to high voltage device. The defects are created during the manufacturing processes of the devices and are prone to high-electric-field-induced PD due to the low permittivity and low breakdown strength of the gaseous medium filling the defects. A contemporary approach of mitigating PD by neutralizing electric fields in high power density applications is introduced in this study. To neutralize the locally enhanced electric fields that occur around the triple points, airgaps, sharp edges, and bubbles, electrets are developed and incorporated into high voltage applications. Electrets are electric fields emitting dielectric materials that are embedded with electrical charges on the surface and in bulk. In this study, electrets are fabricated by electrically charging polyvinylidene difluoride (PVDF) films based on the widely used triode corona discharge method. To investigate the PD mitigation performance of the fabricated electret films, a series of PD experiments are conducted on both the charged and uncharged PVDF films under square voltage stimuli that represent PWM waveform. In addition to the use of single layer electrets, multiple layers of electrets are also experimented with to mitigate PD caused by higher system voltages. The electret-based approach shows great promise in mitigating PD by neutralizing the local electric field. The results of the PD measurements suggest that the development of an ultimate solution to the decades-long dielectric challenge would be possible with further developments in the fabrication process of electrets.

Keywords: electrets, high power density, partial discharge, triode corona discharge

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Authors: John T. Leman, James Gibson, Peter J. Bonitatibus

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There have been no potential clinically translatable developments of intravenous CT contrast materials over decades, and iodinated contrast agents (ICA) remain the only FDA-approved media for CT. Small molecule ICA used to highlight vascular anatomy have weak CT signals in large-to-obese patients due to their rapid redistribution from plasma into interstitial fluid, thereby diluting their intravascular concentration, and because of a mismatch of iodine’s K-edge and the high kVp settings needed to image this patient population. The use of ICA is also contraindicated in a growing population of renally impaired patients who are hypersensitive to these contrast agents; a transformative intravenous contrast agent with improved capabilities is urgently needed. Tantalum oxide nanoparticles (TaO NPs) with zwitterionic siloxane polymer coatings have high potential as clinically translatable general-purpose CT contrast agents because of (1) substantially improved imaging efficacy compared to ICA in swine/phantoms emulating medium-sized and larger adult abdomens and superior thoracic vascular contrast enhancement of thoracic arteries and veins in rabbit, (2) promising biological safety profiles showing near-complete renal clearance and low tissue retention at 3x anticipated clinical dose (ACD), and (3) clinically acceptable physiochemical parameters as concentrated bulk solutions(250-300 mgTa/mL). Here, we review requirements for general-purpose intravenous CT contrast agents in terms of patient safety, X-ray attenuating properties and contrast-producing capabilities, and physicochemical and pharmacokinetic properties. We report the current status of a TaO NP-based contrast agent, including chemical process technology developments and results of newly defined scaled-up processes for NP synthesis and purification, yielding reproducible formulations with appropriate size and concentration specifications. We discuss recent results of recent pre-clinical in vitro immunology, non-GLP high dose tolerability in rats (10x ACD), non-GLP long-term biodistribution in rats at 3x ACD, and non-GLP repeat dose in rats at ACD. We also include a discussion of NP characterization, in particular size-stability testing results under accelerated conditions (37C), and insights into TaO NP purity, surface structure, and bonding of the zwitterionic siloxane polymer coating by multinuclear (1H, 13C, 29Si) and multidimensional (2D) solution NMR spectroscopy.

Keywords: nanoparticle, imaging, diagnostic, process technology, nanoparticle characterization

Procedia PDF Downloads 37

Authors: Tsedekech Gebremeskel Weldmichael, Tamas Szegi, Lubangakene Denish, Ravi Kumar Gangwar, Erika Micheli, Barbara Simon

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Following the 1992 Earth Summit in Rio de Janeiro, soil biodiversity has been recognized globally as a crucial player in guaranteeing the functioning of soil and a provider of several ecosystem services essential for human well-being. The microbial fraction of the soil is a vital component of soil fertility as soil microbes play key roles in soil aggregate formation, nutrient cycling, humification, and degradation of pollutants. Soil fauna, such as earthworms, have huge impacts on soil organic matter dynamics, nutrient cycling, and infiltration and distribution of water in the soil. Currently, land-use change has been a global concern as evidence accumulates that it adversely affects soil biodiversity and the associated ecosystem goods and services. In this study, we examined the patterns of soil microbial respiration (SMR) and earthworm (abundance, biomass, and species richness) across three land-use types (grassland, arable land, and forest) in Hungary. The objectives were i) to investigate whether there is a significant difference in SMR and earthworm (abundance, biomass, and species richness) among land-use types. ii) to determine the key soil properties that best predict the variation in SMR and earthworm communities. Soil samples, to a depth of 25 cm, were collected from the surrounding areas of seven soil profiles. For physicochemical parameters, soil organic matter (SOM), pH, CaCO₃, E₄/E₆, available nitrogen (NH₄⁺-N and NO₃⁻-N), potassium (K₂O), phosphorus (P₂O₅), exchangeable Ca²⁺, Mg²⁺, soil moisture content (MC) and bulk density were measured. The analysis of SMR was determined by basal respiration method, and the extraction of earthworms was carried out by hand sorting method as described by ISO guideline. The results showed that there was no statistically significant difference among land-use types in SMR (p > 0.05). However, the highest SMR was observed in grassland soils (11.77 mgCO₂ 50g⁻¹ soil 10 days⁻¹) and lowest in forest soils (8.61 mgCO₂ 50g⁻¹ soil 10 days⁻¹). SMR had strong positive correlations with exchangeable Ca²⁺ (r = 0.80), MC (r = 0.72), and exchangeable Mg²⁺(r = 0.69). We found a pronounced variation in SMR among soil texture classes (p < 0.001), where the highest value in silty clay loam soils and the lowest in sandy soils. This study provides evidence that agricultural activities can negatively influence earthworm communities, in which the arable land had significantly lower earthworm communities compared to forest and grassland respectively. Overall, in our study, land use type had minimal effects on SMR whereas, earthworm communities were profoundly influenced by land-use type particularly agricultural activities related to tillage. Exchangeable Ca²⁺, MC, and texture were found to be the key drivers of the variation in SMR.

Keywords: earthworm community, land use, soil biodiversity, soil microbial respiration, soil property

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Authors: N. Demertzis, J. L. Bowen

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Sepsis is a complex and rapidly evolving condition, resulting from uncontrolled prolonged activation of host immune system due to pathogenic insult. The aim of this study is the development of a multiplex electrochemical sensing platform, capable of detecting both pathogen associated and host immune markers to enable the rapid and definitive diagnosis of sepsis. A combination of aptamers and molecular imprinting approaches have been employed to generate sensing systems for lipopolysaccharide (LPS), c-reactive protein (CRP) and procalcitonin (PCT). Gold working electrodes were mechanically polished and electrochemically cleaned with 0.1 M sulphuric acid using cyclic voltammetry (CV). Following activation, a self-assembled monolayer (SAM) was generated, by incubating the electrodes with a thiolated anti-LPS aptamer / dithiodibutiric acid (DTBA) mixture (1:20). 3-aminophenylboronic acid (3-APBA) in combination with the anti-LPS aptamer was used for the development of the hybrid molecularly imprinted sensor (apta-MIP). Aptasensors, targeting PCT and CRP were also fabricated, following the same approach as in the case of LPS, with mercaptohexanol (MCH) replacing DTBA. In the case of the CRP aptasensor, the SAM was formed following incubation of a 1:1 aptamer: MCH mixture. However, in the case of PCT, the SAM was formed with the aptamer itself, with subsequent backfilling with 1 μM MCH. The binding performance of all systems has been evaluated using electrochemical impedance spectroscopy. The apta-MIP’s polymer thickness is controlled by varying the number of electropolymerisation cycles. In the ideal number of polymerisation cycles, the polymer must cover the electrode surface and create a binding pocket around LPS and its aptamer binding site. Less polymerisation cycles will create a hybrid system which resembles an aptasensor, while more cycles will be able to cover the complex and demonstrate a bulk polymer-like behaviour. Both aptasensor and apta-MIP were challenged with LPS and compared to conventional imprinted (absence of aptamer from the binding site, polymer formed in presence of LPS) and non-imprinted polymers (NIPS, absence of LPS whilst hybrid polymer is formed). A stable LPS aptasensor, capable of detecting down to 5 pg/ml of LPS was generated. The apparent Kd of the system was estimated at 17 pM, with a Bmax of approximately 50 pM. The aptasensor demonstrated high specificity to LPS. The apta-MIP demonstrated superior recognition properties with a limit of detection of 1 fg/ml and a Bmax of 100 pg/ml. The CRP and PCT aptasensors were both able to detect down to 5 pg/ml. Whilst full binding performance is currently being evaluated, there is none of the sensors demonstrate cross-reactivity towards LPS, CRP or PCT. In conclusion, stable aptasensors capable of detecting LPS, PCT and CRP at low concentrations have been generated. The realisation of a multiplex panel such as described herein, will effectively contribute to the rapid, personalised diagnosis of sepsis.

Keywords: aptamer, electrochemical impedance spectroscopy, molecularly imprinted polymers, sepsis

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Authors: Xiaoling Ren, Guidong Yang

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As one of the largest industrial synthetic chemicals in the world, ammonia has the advantages of high energy density, easy liquefaction, and easy transportation, which is widely used in agriculture, chemical industry, energy storage, and other fields. The industrial Haber-Bosch method process for ammonia synthesis is generally conducted under severe conditions. It is essential to develop a green, sustainable strategy for ammonia production to meet the growing demand. In this direction, photocatalytic nitrogen reduction has huge advantages over the traditional, well-established Haber-Bosch process, such as the utilization of natural sun light as the energy source and significantly lower pressure and temperature to affect the reaction process. However, the high activation energy of nitrogen and the low efficiency of photo-generated electron-hole separation in the photocatalyst result in low ammonia production yield. Many researchers focus on improving the catalyst. In addition to modifying the catalyst, improving the dispersion of the catalyst and making full use of active sites are also means to improve the overall catalytic activity. Few studies have been carried out on this, which is the aim of this work. In this work, by making full use of the nitrogen activation ability of WO3-x with defective sites, small size WO3-x photocatalyst with high dispersibility was constructed, while the growth of WO3-x was restricted by using a high specific surface area mesoporous SBA-15 molecular sieve with the regular pore structure as a template. The morphology of pure SBA-15 and WO3-x/SBA-15 was characterized byscanning electron microscopy (SEM). Compared with pure SBA-15, some small particles can be found in the WO3-x/SBA-15 material, which means that WO3-x grows into small particles under the limitation of SBA-15, which is conducive to the exposure of catalytically active sites. To elucidate the chemical nature of the material, the X-ray diffraction (XRD) analysis was conducted. The observed diffraction pattern inWO3-xis in good agreement with that of the JCPDS file no.71-2450. Compared with WO3-x, no new peaks appeared in WO3-x/SBA-15.It can be concluded that WO3-x/SBA-15 was synthesized successfully. In order to provide more active sites, the mass content of WO3-x was optimized. Then the photocatalytic nitrogen reduction performances of above samples were performed with methanol as a hole scavenger. The results show that the overall ammonia production performance of WO3-x/SBA-15 is improved than pure bulk WO3-x. The above results prove that making full use of active sites is also a means to improve overall catalytic activity.This work provides material basis for the design of high-efficiency photocatalytic nitrogen reduction catalysts.

Keywords: ammonia, photocatalytic, nitrogen reduction, WO3-x, high dispersibility

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Authors: Nipa Debnath, Harinarayan Das, Takahiko Kawaguchi, Naonori Sakamoto, Kazuo Shinozaki, Hisao Suzuki, Naoki Wakiya

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Nowadays spinel ferrite magnetic thin films have drawn considerable attention due to their interesting magnetic and electrical properties with enhanced chemical and thermal stability. Spinel ferrite magnetic films can be implemented in magnetic data storage, sensors, and spin filters or microwave devices. It is well established that the structural, magnetic and transport properties of the magnetic thin films are dependent on microstructure. Spinodal decomposition (SD) is a phase separation process, whereby a material system is spontaneously separated into two phases with distinct compositions. The periodic microstructure is the characteristic feature of SD. Thus, SD can be exploited to control the microstructure at the nanoscale level. In bulk spinel ferrites having general formula, MₓFe₃₋ₓ O₄ (M= Co, Mn, Ni, Zn), phase separation via SD has been reported only for cobalt ferrite (CFO); however, long time post-annealing is required to occur the spinodal decomposition. We have found that SD occurs in CoF thin film without using any post-deposition annealing process if we apply magnetic field during thin film growth. Dynamic Aurora pulsed laser deposition (PLD) is a specially designed PLD system through which in-situ magnetic field (up to 2000 G) can be applied during thin film growth. The in-situ magnetic field suppresses the recombination of ions in the plume. In addition, the peak’s intensity of the ions in the spectra of the plume also increases when magnetic field is applied to the plume. As a result, ions with high kinetic energy strike into the substrate. Thus, ion-impingement occurred under magnetic field during thin film growth. The driving force of SD is the ion-impingement towards the substrates that is induced by in-situ magnetic field. In this study, we report about the occurrence of phase separation through SD and evolution of microstructure after phase separation in spinel ferrite thin films. The surface morphology of the phase separated films show checkerboard like domain structure. The cross-sectional microstructure of the phase separated films reveal columnar type phase separation. Herein, the decomposition wave propagates in lateral direction which has been confirmed from the lateral composition modulations in spinodally decomposed films. Large magnetic anisotropy has been found in spinodally decomposed nickel ferrite (NFO) thin films. This approach approves that magnetic field is also an important thermodynamic parameter to induce phase separation by the enhancement of up-hill diffusion in thin films. This thin film deposition technique could be a more efficient alternative for the fabrication of self-organized phase separated thin films and employed in controlling of the microstructure at nanoscale level.

Keywords: Dynamic Aurora PLD, magnetic anisotropy, spinodal decomposition, spinel ferrite thin film

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Authors: Vinu Viswanath, Lawrence Dsouza, Ugo Ravon

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Syngas typically and intermediary gas product has a wide range of application of producing various chemical products, such as mixed alcohols, hydrogen, ammonia, Fischer-Tropsch products methanol, ethanol, aldehydes, alcohols, etc. There are several technologies available for the syngas production. An alternative to the conventional processes an attractive route of utilizing carbon dioxide and methane in equimolar ratio to generate syngas of ratio close to one has been developed which is also termed as Dry Reforming of Methane technology. It also gives the privilege to utilize the greenhouse gases like CO2 and CH4. The dry reforming process is highly endothermic, and indeed, ΔG becomes negative if the temperature is higher than 900K and practically, the reaction occurs at 1000-1100K. At this temperature, the sintering of the metal particle is happening that deactivate the catalyst. However, by using this strategy, the methane is just partially oxidized, and some cokes deposition occurs that causing the catalyst deactivation. The current research work was focused to mitigate the main challenges of dry reforming process such coke deposition, and metal sintering at high temperature.To achieve these objectives, we employed three different strategies of catalyst development. 1) Use of bulk catalysts such as olivine and pyrochlore type materials. 2) Use of metal doped support materials, like spinel and clay type material. 3) Use of core-shell model catalyst. In this approach, a thin layer (shell) of redox metal oxide is deposited over the MgAl2O4 /Al2O3 based support material (core). For the core-shell approach, an active metal is been deposited on the surface of the shell. The shell structure formed is a doped metal oxide that can undergo reduction and oxidation reactions (redox), and the core is an alkaline earth aluminate having a high affinity towards carbon dioxide. In the case of metal-doped support catalyst, the enhanced redox properties of doped CeO2 oxide and CO2 affinity property of alkaline earth aluminates collectively helps to overcome coke formation. For all of the mentioned three strategies, a systematic screening of the metals is carried out to optimize the efficiency of the catalyst. To evaluate the performance of them, the activity and stability test were carried out under reaction conditions of temperature ranging from 650 to 850 ̊C and an operating pressure ranging from 1 to 20 bar. The result generated infers that the core-shell model catalyst showed high activity and better stable DR catalysts under atmospheric as well as high-pressure conditions. In this presentation, we will show the results related to the strategy.

Keywords: carbon dioxide, dry reforming, supports, core shell catalyst

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Authors: Chris Miskelly, Eoin Cunningham, Beatrice Smyth, John. D. Holbrey, Gosia Swadzba-Kwasny, Emily L. Byrne, Yoan Delavoux, Mantian Li.

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Recently, the use of ionic liquids (ILs) for the preparation of lignocellulose derived cellulosic materials as alternatives to petrochemical feedstocks has been the focus of considerable research interest. While the technical viability of IL-based lignocellulose treatment methodologies has been well established, the high cost of reagents inhibits commercial feasibility. This work aimed to assess the technoeconomic viability of the preparation of cellulose rich materials (CRMs) using protic ionic liquids (PILs) synthesized from low cost alkylamines and sulphuric acid. For this purpose, the tertiary alkylamines, triethylamine, and dimethylbutylamine were selected. Bulk scale production cost of the synthesized PILs, triethylammonium hydrogen sulphate and dimetheylbutylammonium hydrogen sulphate, was reported as $0.78 kg-1 to $1.24 kg-1. CRMs were prepared through the treatment of common wheat (Triticum aestivum) straw with these PILs. By controlling treatment parameters, CRMs with a cellulose content of ≥ 80 wt% were prepared. This was achieved using a T. aestivum straw to PIL loading ratio of 1:15 w/w, a treatment duration of 180 minutes, and ethanol as a cellulose antisolvent. Infrared spectra data and decreased onset degradation temperature of CRMs (ΔTONSET ~ 70 °C) suggested the formation of cellulose sulphate esters during treatment. Chemical derivatisation can aid the dispersion of prepared CRMs in non-polar polymer/ composite matrices, but act as a barrier to thermal processing at temperatures above 150 °C. It was also shown that treatment increased the crystallinity of CRMs (ΔCrI ~ 40 %) without altering the native crystalline structure or crystallite size (~ 2.6 nm) of cellulose; peaks associated with the cellulose I crystalline planes (110), (200), and (004) were observed at Bragg angles 16.0 °, 22.5 ° and 35.0 ° respectively. This highlighted the inability of assessed PILs to dissolve crystalline cellulose and was attributed to the high acidity (pKa ~ - 1.92 to - 6.42) of sulphuric acid derived anions. Electron micrographs revealed that the stratified multilayer tissue structure of untreated T. aestivum straw was significantly modified during treatment. T. aestivum straw particles were disassembled during treatment, with prepared CRMs adopting a golden-brown film-like appearance. This work demonstrated the degradation of non-cellulosic fractions of lignocellulose without dissolution of cellulose. It is the first to report on the derivatisation of cellulose during treatment with protic hydrogen sulphate ionic liquids, and the potential implications of this with reference to biopolymer feedstock preparation.

Keywords: cellulose, extraction, protic ionic liquids, esterification, thermal stability, waste valorisation, biopolymer feedstock

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Authors: C. Fornacelli, P. Colomban, E. Mugnaioli, I. Memmi Turbanti

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When semiconductor particles are reduced in scale to nanometer dimension, their optical and electro-optical properties strongly differ from those of bulk crystals of the same composition. Since sampling is often not allowed concerning cultural heritage artefacts, the potentialities of two non-invasive techniques, such as Raman and Fiber Optic Reflectance Spectroscopy (FORS), have been investigated and the results of the analysis on some original glasses of different colours (from yellow to orange and deep red) and periods (from the second decade of the 20th century to present days) are reported in the present study. In order to evaluate the potentialities of the application of non-invasive techniques to the investigation of the structure and distribution of nanoparticles dispersed in a glass matrix, Scanning Electron Microscopy (SEM) and energy-disperse spectroscopy (EDS) mapping, together with Transmission Electron Microscopy (TEM) and Electron Diffraction Tomography (EDT) have also been used. Raman spectroscopy allows a fast and non-destructive measure of the quantum dots composition and size, thanks to the evaluation of the frequencies and the broadening/asymmetry of the LO phonons bands, respectively, though the important role of the compressive strain arising from the glass matrix and the possible diffusion of zinc from the matrix to the nanocrystals should be taken into account when considering the optical-phonons frequency values. The incorporation of Zn has been assumed by an upward shifting of the LO band related to the most abundant anion (S or Se), while the role of the surface phonons as well as the confinement-induced scattering by phonons with a non-zero wavevectors on the Raman peaks broadening has been verified. The optical band gap varies from 2.42 eV (pure CdS) to 1.70 eV (CdSe). For the compositional range between 0.5≤x≤0.2, the presence of two absorption edges has been related to the contribution of both pure CdS and the CdSxSe1-x solid solution; this particular feature is probably due to the presence of unaltered cubic zinc blende structures of CdS that is not taking part to the formation of the solid solution occurring only between hexagonal CdS and CdSe. Moreover, the band edge tailing originating from the disorder due to the formation of weak bonds and characterized by the Urbach edge energy has been studied and, together with the FWHM of the Raman signal, has been assumed as a good parameter to evaluate the degree of topological disorder. SEM-EDS mapping showed a peculiar distribution of the major constituents of the glass matrix (fluxes and stabilizers), especially concerning those samples where a layered structure has been assumed thanks to the spectroscopic study. Finally, TEM-EDS and EDT were used to get high-resolution information about nanocrystals (NCs) and heterogeneous glass layers. The presence of ZnO NCs (< 4 nm) dispersed in the matrix has been verified for most of the samples, while, for those samples where a disorder due to a more complex distribution of the size and/or composition of the NCs has been assumed, the TEM clearly verified most of the assumption made by the spectroscopic techniques.

Keywords: CdSxSe1-x, EDT, glass, spectroscopy, TEM-EDS

Procedia PDF Downloads 299

Authors: Riya Bose, Ashok Bera, Manas R. Parida, Anirudhha Adhikari, Basamat S. Shaheen, Erkki Alarousu, Jingya Sun, Tom Wu, Osman M. Bakr, Omar F. Mohammed

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This work reports visualization of charge carrier dynamics on the surface of copper indium gallium selenide (CIGSe) nanocrystals in real space and time using four-dimensional scanning ultrafast electron microscopy (4D S-UEM) and correlates it with the optoelectronic properties of the nanocrystals. The surface of the nanocrystals plays a key role in controlling their applicability for light emitting and light harvesting purposes. Typically for quaternary systems like CIGSe, which have many desirable attributes to be used for optoelectronic applications, relative abundance of surface trap states acting as non-radiative recombination centre for charge carriers remains as a major bottleneck preventing further advancements and commercial exploitation of these nanocrystals devices. Though ultrafast spectroscopic techniques allow determining the presence of picosecond carrier trapping channels, because of relative larger penetration depth of the laser beam, only information mainly from the bulk of the nanocrystals is obtained. Selective mapping of such ultrafast dynamical processes on the surfaces of nanocrystals remains as a key challenge, so far out of reach of purely optical probing time-resolved laser techniques. In S-UEM, the optical pulse generated from a femtosecond (fs) laser system is used to generate electron packets from the tip of the scanning electron microscope, instead of the continuous electron beam used in the conventional setup. This pulse is synchronized with another optical excitation pulse that initiates carrier dynamics in the sample. The principle of S-UEM is to detect the secondary electrons (SEs) generated in the sample, which is emitted from the first few nanometers of the top surface. Constructed at different time delays between the optical and electron pulses, these SE images give direct and precise information about the carrier dynamics on the surface of the material of interest. In this work, we report selective mapping of surface dynamics in real space and time of CIGSe nanocrystals applying 4D S-UEM. We show that the trap states can be considerably passivated by ZnS shelling of the nanocrystals, and the carrier dynamics can be significantly slowed down. We also compared and discussed the S-UEM kinetics with the carrier dynamics obtained from conventional ultrafast time-resolved techniques. Additionally, a direct effect of the state trap removal can be observed in the enhanced photoresponse of the nanocrystals after shelling. Direct observation of surface dynamics will not only provide a profound understanding of the photo-physical mechanisms on nanocrystals’ surfaces but also enable to unlock their full potential for light emitting and harvesting applications.

Keywords: 4D scanning ultrafast microscopy, charge carrier dynamics, nanocrystals, optoelectronics, surface passivation, trap states

Procedia PDF Downloads 295

Authors: Sadat Sembatya

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Tantalum metal is used in addressing capacitance challenge in the 21st-century technology growth. Tantalum is rarely found in its elemental form. Hence it’s often found with niobium and the radioactive elements of thorium and uranium. Industrial processes are required to extract pure tantalum. Its deposits are mainly oxide associated and exist in Ta-Nb oxides such as tapiolite, wodginite, ixiolite, rutile and pyrochlore-supergroup minerals are of minor importance. The stability and chemical inertness of tantalum makes it a valuable substance for laboratory equipment and a substitute for platinum. Each period of Tantalum ore formation is characterized by specific mineralogical and geochemical features. Compositions of Columbite-Group Minerals (CGM) are variable: Fe-rich types predominate in the Man Shield (Sierra Leone), the Congo Craton (DR Congo), the Kamativi Belt (Zimbabwe) and the Jos Plateau (Nigeria). Mn-rich columbite-tantalite is typical of the Alto Ligonha Province (Mozambique), the Arabian-Nubian Shield (Egypt, Ethiopia) and the Tantalite Valley pegmatites (southern Namibia). There are large compositional variations through Fe-Mn fractionation, followed by Nb-Ta fractionation. These are typical for pegmatites usually associated with very coarse quartz-feldspar-mica granites. They are young granitic systems of the Kibara Belt of Central Africa and the Older Granites of Nigeria. Unlike ‘simple’ Be-pegmatites, most Ta-Nb rich pegmatites have the most complex zoning. Hence we need systematic exploration tools to find and rapidly assess the potential of different pegmatites. The pegmatites exist as known deposits (e.g., abandoned mines) and the exposed or buried pegmatites. We investigate rocks and minerals to trace for the possibility of the effect of hydrothermal alteration mainly for exposed pegmatites, do mineralogical study to prove evidence of gradual replacement and geochemistry to report the availability of trace elements which are good indicators of mineralisation. Pegmatites are not good geophysical responders resulting to the exclusion of the geophysics option. As for more advanced prospecting, we bulk samples from different zones first to establish their grades and characteristics, then make a pilot test plant because of big samples to aid in the quantitative characterization of zones, and then drill to reveal distribution and extent of different zones but not necessarily grade due to nugget effect. Rapid assessment tools are needed to assess grade and degree of fractionation in order to ‘rule in’ or ‘rule out’ a given pegmatite for future work. Pegmatite exploration is also unique, high risk and expensive hence right traceability system and certification for 3Ts are highly needed.

Keywords: exploration, mineralogy, pegmatites, tantalum

Procedia PDF Downloads 149

Authors: Dina Kon Mushid, Sage Ngoie, Tshimbalanga Madiba, Kabutakapua Kakanda

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Slope stability assessment is still the biggest challenge in mining activities and civil engineering structures. The slope in an opencast mine frequently reaches multiple weak layers that lead to the instability of the pit. Faults and soft layers throughout the rock would increase weathering and erosion rates. Therefore, it is essential to investigate the stability of the complex strata to figure out how stable they are. In the Dikuluwe-Mashamba (DIMA) area, the lithology of the stratum is a set of metamorphic rocks whose parent rocks are sedimentary rocks with a low degree of metamorphism. Thus, due to the composition and metamorphism of the parent rock, the rock formation is different in hardness and softness, which means that when the content of dolomitic and siliceous is high, the rock is hard. It is softer when the content of argillaceous and sandy is high. Therefore, from the vertical direction, it appears as a weak and hard layer, and from the horizontal direction, it seems like a smooth and hard layer in the same rock layer. From the structural point of view, the main structures in the mining area are the Dikuluwe dipping syncline and the Mashamba dipping anticline, and the occurrence of rock formations varies greatly. During the folding process of the rock formation, the stress will concentrate on the soft layer, causing the weak layer to be broken. At the same time, the phenomenon of interlayer dislocation occurs. This article aimed to evaluate the stability of metasedimentary rocks of the Dikuluwe-Mashamba (DIMA) open-pit mine using limit equilibrium and stereographic methods Based on the presence of statistical structural planes, the stereographic projection was used to study the slope's stability and examine the discontinuity orientation data to identify failure zones along the mine. The results revealed that the slope angle is too steep, and it is easy to induce landslides. The numerical method's sensitivity analysis showed that the slope angle and groundwater significantly impact the slope safety factor. The increase in the groundwater level substantially reduces the stability of the slope. Among the factors affecting the variation in the rate of the safety factor, the bulk density of soil is greater than that of rock mass, the cohesion of soil mass is smaller than that of rock mass, and the friction angle in the rock mass is much larger than that in the soil mass. The analysis showed that the rock mass structure types are mostly scattered and fragmented; the stratum changes considerably, and the variation of rock and soil mechanics parameters is significant.

Keywords: slope stability, weak layer, safety factor, limit equilibrium method, stereography method

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Authors: N. Renuka, R. Ramesh Babu, N. Vijayan

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Ion beams play a significant role in the process of tuning the properties of materials. Based on the radiation behavior, the engineering materials are categorized into two different types. The first one comprises organic solids which are sensitive to the energy deposited in their electronic system and the second one comprises metals which are insensitive to the energy deposited in their electronic system. However, exposure to swift heavy ions alters this general behavior. Depending on the mass, kinetic energy and nuclear charge, an ion can produce modifications within a thin surface layer or it can penetrate deeply to produce long and narrow distorted area along its path. When a high energetic ion beam impinges on a material, it causes two different types of changes in the material due to the columbic interaction between the target atom and the energetic ion beam: (i) inelastic collisions of the energetic ion with the atomic electrons of the material; and (ii) elastic scattering from the nuclei of the atoms of the material, which is extremely responsible for relocating the atoms of matter from their lattice position. The exposure of the heavy ions renders the material return to equilibrium state during which the material undergoes surface and bulk modifications which depends on the mass of the projectile ion, physical properties of the target material, its energy, and beam dimension. It is well established that electronic stopping power plays a major role in the defect creation mechanism provided it exceeds a threshold which strongly depends on the nature of the target material. There are reports available on heavy ion irradiation especially on crystalline materials to tune their physical and chemical properties. L-Arginine Acetate [LAA] is a potential semi-organic nonlinear optical crystal and its optical, mechanical and thermal properties have already been reported The main objective of the present work is to enhance or tune the structural and optical properties of LAA single crystals by heavy ion irradiation. In the present study, a potential nonlinear optical single crystal, L-arginine acetate (LAA) was grown by slow evaporation solution growth technique. The grown LAA single crystal was irradiated with oxygen ions at the dose rate of 600 krad and 1M rad in order to tune the structural and optical properties. The structural properties of pristine and oxygen ions irradiated LAA single crystals were studied using Powder X- ray diffraction and Fourier Transform Infrared spectral studies which reveal the structural changes that are generated due to irradiation. Optical behavior of pristine and oxygen ions irradiated crystals is studied by UV-Vis-NIR and photoluminescence analyses. From this investigation we can concluded that oxygen ions irradiation modifies the structural and optical properties of LAA single crystals.

Keywords: heavy ion irradiation, NLO single crystal, photoluminescence, X-ray diffractometer

Procedia PDF Downloads 254

Authors: Zélia Maria Da Costa Ludwig, Maria José Valenzuela Bell, Geraldo Henriques Da Silva, Thales Alves Faraco, Victor Rocha Da Silva, Daniel Rotmeister Teixeira, Vírgilio De Carvalho Dos Anjos, Valdemir Ludwig

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Advances in telecommunications grow with the development of optical amplifiers based on rare earth ions. The focus has been concentrated in silicate glasses although their amplified spontaneous emission is limited to a few tens of nanometers (~ 40nm). Recently, phosphate glasses have received great attention due to their potential application in optical data transmission, detection, sensors and laser detector, waveguide and optical fibers, besides its excellent physical properties such as high thermal expansion coefficients and low melting temperature. Compared with the silica glasses, phosphate glasses provide different optical properties such as, large transmission window of infrared, and good density. Research on the improvement of physical and chemical durability of phosphate glass by addition of heavy metals oxides in P2O5 has been performed. The addition of Na2O further improves the solubility of rare earths, while increasing the Al2O3 links in the P2O5 tetrahedral results in increased durability and aqueous transition temperature and a decrease of the coefficient of thermal expansion. This work describes the structural and spectroscopic characterization of a phosphate glass matrix doped with different Er (Erbium) concentrations. The phosphate glasses containing Er3+ ions have been prepared by melt technique. A study of the optical absorption, luminescence and lifetime was conducted in order to characterize the infrared emission of Er3+ ions at 1540 nm, due to the radiative transition 4I13/2 → 4I15/2. Our results indicate that the present glass is a quite good matrix for Er3+ ions, and the quantum efficiency of the 1540 nm emission was high. A quenching mechanism for the mentioned luminescence was not observed up to 2,0 mol% of Er concentration. The Judd-Ofelt parameters, radiative lifetime and quantum efficiency have been determined in order to evaluate the potential of Er3+ ions in new phosphate glass. The parameters follow the trend as Ω2 > Ω4 > Ω6. It is well known that the parameter Ω2 is an indication of the dominant covalent nature and/or structural changes in the vicinity of the ion (short range effects), while Ω4 and Ω6 intensity parameters are long range parameters that can be related to the bulk properties such as viscosity and rigidity of the glass. From the PL measurements, no red or green upconversion was measured when pumping the samples with laser excitation at 980 nm. As future prospects: Synthesize this glass system with silver in order to determine the influence of silver nanoparticles on the Er3+ ions.

Keywords: phosphate glass, erbium, luminescence, glass system

Procedia PDF Downloads 510

Authors: Halima Sadia Qureshi, Urooj Sadiq, Noshi Eram Zaman

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The goal of this study was to see how cognitive behavior hypnotherapy affected nonsuicidal self-injury. DSM 5 invites the researchers to explore the newly added condition under the chapter of conditions under further study named Nonsuicidal self-injury disorder. To date, no empirical sound intervention has been proven effective for NSSI as given in DSM 5. Nonsuicidal self-injury is defined by DSM 5 as harming one's self physically, without suicidal intention. Around 7.6% of teenagers are expected to fulfill the NSSI disorder criteria. 3 Adolescents, particularly university students, account for around 87 percent of self-harm studies. Furthermore, one of the risks associated with NSSI is an increased chance of suicide attempts, and in most cases, the cycle repeats again. 6 The emotional and psychological components of the illness might lead to suicide, either intentionally or unintentionally. 7 According to a research done at a Pakistani military hospital, over 80% of participants had no intention of committing suicide. Furthermore, it has been determined that improvements in NSSI prevention and intervention are necessary as a stand-alone strategy. The quasi-experimental study took place in Islamabad and Rawalpindi, Pakistan, from May 2019 to April 2020 and included students aged 18 to 25 years old from several institutions and colleges in the twin cities. According to the Diagnostic and Statistical Manual of Mental Disorders 5th edition, the individuals were assessed for >2 episodes without suicidal intent using the intentional self-harm questionnaire. The Clinician Administered Nonsuicidal Self-Injury Disorder Index (CANDI) was used to assess the individual for NSSI condition. Symptom checklist-90 (SCL-90) was used to screen the participants for differential diagnosis. Mclean Screening Instrument for Borderline Personality Disorder (MSI-BPD) was used to rule out the BPD cases. The selected participants, n=106 from the screening sample of 600, were selected. They were further screened to meet the inclusion and exclusion criteria, and the total of n=71 were split into two groups: intervention and control. The intervention group received cognitive behavior hypnotherapy for the next three months, whereas the control group received no treatment. After the period of three months, both the groups went through the post assessment, and after the three months’ period, follow-up assessment was conducted. The groups were evaluated, and SPSS 25 was used to analyse the data. The results showed that each of the two groups had 30 (50 percent) of the 60 participants. There were 41 males (68 percent) and 19 girls (32 percent) in all. The bulk of the participants were between the ages of 21 and 23. (48 percent). Self-harm events were reported by 48 (80 percent) of the pupils, and suicide ideation was found in 6 (ten percent). In terms of pre- and post-intervention values (d=4.90), post-intervention and follow-up assessment values (d=0.32), and pre-intervention and follow-up values (d=5.42), the study's effect size was good. The comparison of treatment and no-treatment groups revealed that treatment was more successful than no-treatment, F (1, 58) = 53.16, p.001. The results reveal that the treatment manual of CBH is effective for Nonsuicidal self-injury disorder.

Keywords: NSSI, nonsuicidal self injury disorder, self-harm, self-injury, Cognitive behaviour hypnotherapy, CBH

Procedia PDF Downloads 182

Authors: Dorottya Guban, Irina Borbath, Istvan Bakos, Peter Nemeth, Andras Tompos

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One of the greatest challenges of the implementation of polymer electrolyte membrane fuel cells (PEMFCs) is to find active and durable electrocatalysts. The cell performance is always limited by the oxygen reduction reaction (ORR) on the cathode since it is at least 6 orders of magnitude slower than the hydrogen oxidation on the anode. Therefore high loading of Pt is required. Catalyst corrosion is also more significant on the cathode, especially in case of mobile applications, where rapid changes of loading have to be tolerated. Pt-Sn bulk alloys and SnO2-decorated Pt3Sn nanostructures are among the most studied bimetallic systems for fuel cell applications. Exclusive formation of supported Sn-Pt alloy phases with different Pt/Sn ratios can be achieved by using controlled surface reactions (CSRs) between hydrogen adsorbed on Pt sites and tetraethyl tin. In this contribution our results for commercial and a home-made 20 wt.% Pt/C catalysts modified by tin anchoring via CSRs are presented. The parent Pt/C catalysts were synthesized by modified NaBH4-assisted ethylene-glycol reduction method using ethanol as a solvent, which resulted either in dispersed and highly stable Pt nanoparticles or evenly distributed raspberry-like agglomerates according to the chosen synthesis parameters. The 20 wt.% Pt/C catalysts prepared that way showed improved electrocatalytic performance in the ORR and stability in comparison to the commercial 20 wt.% Pt/C catalysts. Then, in order to obtain Sn-Pt/C catalysts with Pt/Sn= 3 ratio, the Pt/C catalysts were modified with tetraethyl tin (SnEt4) using three and five consecutive tin anchoring periods. According to in situ XPS studies in case of catalysts with highly dispersed Pt nanoparticles, pre-treatment in hydrogen even at 170°C resulted in complete reduction of the ionic tin to Sn0. No evidence of the presence of SnO2 phase was found by means of the XRD and EDS analysis. These results demonstrate that the method of CSRs is a powerful tool to create Pt-Sn bimetallic nanoparticles exclusively, without tin deposition onto the carbon support. On the contrary, the XPS results revealed that the tin-modified catalysts with raspberry-like Pt agglomerates always contained a fraction of non-reducible tin oxide. At the same time, they showed increased activity and long-term stability in the ORR than Pt/C, which was assigned to the presence of SnO2 in close proximity/contact with Pt-Sn alloy phase. It has been demonstrated that the content and dispersion of the fcc Pt3Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. The bimetallic catalysts displayed an outstanding performance in the ORR. The preparation of a highly dispersed 20Pt/C catalyst permits to decrease the Pt content without relevant decline in the electrocatalytic performance of the catalysts.

Keywords: anode catalyst, cathode catalyst, controlled surface reactions, oxygen reduction reaction, PtSn/C electrocatalyst

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Authors: M. Shopska, D. Paneva, G. Kadinov, Z. Cherkezova-Zheleva, I. Mitov

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The iron containing materials are used as catalysts in different processes. The chemical methods of their synthesis use toxic and expensive chemicals; sophisticated devices; energy consumption processes that raise their cost. Besides, dangerous waste products are formed. At present time such syntheses are out of date and wasteless technologies are indispensable. The bioinspired technologies are consistent with the ecological requirements. Different microorganisms participate in the biomineralization of the iron and some phytochemicals are involved, too. The methods for biogenic production of iron containing materials are clean, simple, nontoxic, realized at ambient temperature and pressure, cheaper. The biogenic iron materials embrace different iron compounds. Due to their origin these substances are nanosized, amorphous or poorly crystalline, porous and have number of useful properties like SPM, high magnetism, low toxicity, biocompatibility, absorption of microwaves, high surface area/volume ratio, active sites on the surface with unusual coordination that distinguish them from the bulk materials. The biogenic iron materials are applied in the heterogeneous catalysis in different roles - precursor, active component, support, immobilizer. The application of biogenic iron oxide materials gives rise to increased catalytic activity in comparison with those of abiotic origin. In our study we investigated the catalytic behavior of biomasses obtained by cultivation of Leptothrix bacteria in three nutrition media – Adler, Fedorov, and Lieske. The biomass composition was studied by Moessbauer spectroscopy and transmission IRS. Catalytic experiments on CO oxidation were carried out using in situ DRIFTS. Our results showed that: i) the used biomasses contain α-FeOOH, γ-FeOOH, γ-Fe2O3 in different ratios; ii) the biomass formed in Adler medium contains γ-FeOOH as main phase. The CO conversion was about 50% as evaluated by decreased integrated band intensity in the gas mixture spectra during the reaction. The main phase in the spent sample is γ-Fe2O3; iii) the biomass formed in Lieske medium contains α-FeOOH. The CO conversion was about 20%. The main phase in the spent sample is α-Fe2O3; iv) the biomass formed in Fedorov medium contains γ-Fe2O3 as main phase. CO conversion in the test reaction was about 19%. The results showed that the catalytic activity up to 200°C resulted predominantly from α-FeOOH and γ-FeOOH. The catalytic activity at temperatures higher than 200°C was due to the formation of γ-Fe2O3. The oxyhydroxides, which are the principal compounds in the biomass, have low catalytic activity in the used reaction; the maghemite has relatively good catalytic activity; the hematite has activity commensurate with that of the oxyhydroxides. Moreover it can be affirmed that catalytic activity is inherent in maghemite, which is obtained by transformation of the biogenic lepidocrocite, i.e. it has biogenic precursor.

Keywords: nanosized biogenic iron compounds, catalytic behavior in reaction of CO oxidation, in situ DRIFTS, Moessbauer spectroscopy

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Authors: Olga Yu Kurapova, Alexander V. Shorokhov, Vladimir G. Konakov

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Nowadays, due to their exceptional anion conductivity at high temperatures cubic zirconia solid solutions, stabilized by rare-earth and alkaline-earth metal oxides, are widely used as a solid electrolyte (SE) materials in different electrochemical devices such as gas sensors, oxygen pumps, solid oxide fuel cells (SOFC), etc. Nowadays the intensive studies are carried out in a field of novel fully stabilized zirconia based SE development. The use of precursor powders for SE manufacturing allows predetermining the microstructure, electrical and sensor characteristics of zirconia based ceramics used as SE. Thus the goal of the present work was the investigation of the effect of precursor powder size on the electrical and sensor characteristics of fully stabilized zirconia-based solid electrolytes with compositions of 0,08Y2O3∙0,92ZrO2 (YSZ), 0,06Ce2O3∙ 0,06Y2O3∙0,88ZrO2 and 0,09Ce2O3∙0,06Y2O3-0,85ZrO2. The synthesis of precursors powders with different mean particle size was performed by sol-gel synthesis in the form of reversed co-precipitation from aqueous solutions. The cakes were washed until the neutral pH and pan-dried at 110 °С. Also, YSZ ceramics was obtained by conventional solid state synthesis including milling into a planetary mill. Then the powder was cold pressed into the pellets with a diameter of 7.2 and ~4 mm thickness at P ~16 kg/cm2 and then hydrostatically pressed. The pellets were annealed at 1600 °С for 2 hours. The phase composition of as-synthesized SE was investigated by X-Ray photoelectron spectroscopy ESCA (spectrometer ESCA-5400, PHI) X-ray diffraction analysis - XRD (Shimadzu XRD-6000). Following galvanic cell О2 (РО2(1)), Pt | SE | Pt, (РО2(2) = 0.21 atm) was used for SE sensor properties investigation. The value of РО2(1) was set by mixing of O2 and N2 in the defined proportions with the accuracy of  5%. The temperature was measured by Pt/Pt-10% Rh thermocouple, The cell electromotive force (EMF) measurement was carried out with ± 0.1 mV accuracy. During the operation at the constant temperature, reproducibility was better than 5 mV. Asymmetric potential measured for all SE appeared to be negligible. It was shown that the resistivity of YSZ ceramics decreases in about two times upon the mean agglomerates decrease from 200-250 to 40 nm. It is likely due to the both surface and bulk resistivity decrease in grains. So the overall decrease of grain size in ceramic SE results in the significant decrease of the total ceramics resistivity allowing sensor operation at lower temperatures. For the SE manufactured the estimation of oxygen ion transfer number tion was carried out in the range 600-800 °С. YSZ ceramics manufactured from powders with the mean particle size 40-140 nm, shows the highest values i.e. 0.97-0.98. SE manufactured from precursors with the mean particle size 40-140 nm shows higher sensor characteristic i.e. temperature and oxygen concentration EMF dependencies, EMF (ENernst - Ereal), tion, response time, then ceramics, manufactured by conventional solid state synthesis.

Keywords: oxygen sensors, precursor powders, sol-gel synthesis, stabilized zirconia ceramics

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Authors: Hossein Hassani, Ali Rezaei

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Heavy metals are naturally occurring elements that have a high atomic weight and a density at least five times greater than that of water. Their multiple industrial, domestic, agricultural, medical, and technological applications have led to their wide distribution in the environment, raising concerns over their potential effects on human health and the environment. Environmental protection against various pollutants, such as heavy metals formed by industries, mines and modern technologies, is a concern for researchers and industry. In order to assess the contamination of soils the distribution and environmental behavior have been investigated. Jajarm bauxite mine, the most important deposits have been discovered in Iran, which is about 22 million tons of reserve, and is the main mineral of the Diaspora. With a view to estimate the heavy metals ratio of the Jajarm bauxite mine area and to evaluate the pollution level, 50 samples have been collected and have been analyzed for the heavy metals of As, Cd, Cu, Hg, Ni and Pb with the help of Inductively Coupled Plasma-Mass Spectrometer (ICP- MS). In this study, we have dealt with determining evaluation criteria including contamination factor (CF), average concentration (AV), enrichment factor (EF) and geoaccumulation index (GI) to assess the risk of pollution from heavy metals(As, Cd, Cu, Hg, Ni and Pb) in Jajarm bauxite mine. In the samples of the studied, the average of recorded concentration of elements for Arsenic, Cadmium, Copper, Mercury, Nickel and Lead are 18, 0.11, 12, 0.07, 58 and 51 (mg/kg) respectively. The comparison of the heavy metals concentration average and the toxic potential in the samples has shown that an average with respect to the world average of the uncontaminated soil amounts. The average of Pb and As elements shows a higher quantity with respect to the world average quantity. The pollution factor for the study elements has been calculated on the basis of the soil background concentration and has been categorized on the basis of the uncontaminated world soil average with respect to the Hakanson classification. The calculation of the corrected pollutant degree shows the degree of the bulk intermediate pollutant (1.55-2.0) for the average soil sampling of the study area which is on the basis of the background quantity and the world average quantity of the uncontaminated soils. The provided conclusion from calculation of the concentrated factor, for some of the samples show that the average of the lead and arsenic elements stations are more than the background values and the unnatural metal concentration are covered under the study area, That's because the process of mining and mineral extraction. Given conclusion from the calculation of Geoaccumulation index of the soil sampling can explain that the copper, nickel, cadmium, arsenic, lead and mercury elements are Uncontamination. In general, the results indicate that the Jajarm bauxite mine of heavy metal pollution is uncontaminated area and extract the mineral from the mine, not create environmental hazards in the region.

Keywords: enrichment factor, geoaccumulation index, heavy metals, Jajarm bauxite mine, pollution

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Authors: Ramzi Farra, Detre Teschner, Marc Willinger, Robert Schlögl

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Introduction: The conventional approach of characterizing solid catalysts under static conditions, i.e., before and after reaction, does not provide sufficient knowledge on the physicochemical processes occurring under dynamic conditions at the molecular level. Hence, the necessity of improving new in situ characterizing techniques with the potential of being used under real catalytic reaction conditions is highly desirable. In situ Prompt Gamma Activation Analysis (PGAA) is a rapidly developing chemical analytical technique that enables us experimentally to assess the coverage of surface species under catalytic turnover and correlate these with the reactivity. The catalytic HCl oxidation (Deacon reaction) over bulk ceria will serve as our example. Furthermore, the in situ Transmission Electron Microscopy is a powerful technique that can contribute to the study of atmosphere and temperature induced morphological or compositional changes of a catalyst at atomic resolution. The application of such techniques (PGAA and TEM) will pave the way to a greater and deeper understanding of the dynamic nature of active catalysts. Experimental/Methodology: In situ Prompt Gamma Activation Analysis (PGAA) experiments were carried out to determine the Cl uptake and the degree of surface chlorination under reaction conditions by varying p(O2), p(HCl), p(Cl2), and the reaction temperature. The abundance and dynamic evolution of OH groups on working catalyst under various steady-state conditions were studied by means of in situ FTIR with a specially designed homemade transmission cell. For real in situ TEM we use a commercial in situ holder with a home built gas feeding system and gas analytics. Conclusions: Two complimentary in situ techniques, namely in situ PGAA and in situ FTIR were utilities to investigate the surface coverage of the two most abundant species (Cl and OH). The OH density and Cl uptake were followed under multiple steady-state conditions as a function of p(O2), p(HCl), p(Cl2), and temperature. These experiments have shown that, the OH density positively correlates with the reactivity whereas Cl negatively. The p(HCl) experiments give rise to increased activity accompanied by Cl-coverage increase (opposite trend to p(O2) and T). Cl2 strongly inhibits the reaction, but no measurable increase of the Cl uptake was found. After considering all previous observations we conclude that only a minority of the available adsorption sites contribute to the reactivity. In addition, the mechanism of the catalysed reaction was proposed. The chlorine-oxygen competition for the available active sites renders re-oxidation as the rate-determining step of the catalysed reaction. Further investigations using in situ TEM are planned and will be conducted in the near future. Such experiments allow us to monitor active catalysts at the atomic scale under the most realistic conditions of temperature and pressure. The talk will shed a light on the potential and limitations of in situ PGAA and in situ TEM in the study of catalyst dynamics.

Keywords: CeO2, deacon process, in situ PGAA, in situ TEM, in situ FTIR

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Authors: Ahlad Neti, Elisa Arch, Martha Hall

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Studies have shown that individuals who use Ankle-Foot-Orthoses (AFOs) have a high level of dissatisfaction regarding their current AFOs. Studies point to the focus on technical design with little attention given to the user perspective as a source of AFO designs that leave users dissatisfied. To design a new AFO that satisfies users and thereby improves their quality of life, the reasons for their dissatisfaction and their wants and needs for an improved AFO design must be identified. There has been little research into the user perspective on AFO use and desired improvements, so the relationship between AFO design and satisfaction in daily use must be assessed to develop appropriate metrics and constraints prior to designing a novel AFO. To assess the user perspective on AFO design, structured interviews were conducted with 7 individuals (average age of 64.29±8.81 years) who use AFOs. All interviews were transcribed and coded to identify common themes using Grounded Theory Method in NVivo 12. Qualitative analysis of these results identified sources of user dissatisfaction such as heaviness, bulk, and uncomfortable material and overall needs and wants for an AFO. Beyond the user perspective, certain objective factors must be considered in the construction of metrics and constraints to ensure that the AFO fulfills its medical purpose. These more objective metrics are rooted in a common medical device market and technical standards. Given the large body of research concerning these standards, these objective metrics and constraints were derived through a literature review. Through these two methods, a comprehensive list of metrics and constraints accounting for both the user perspective on AFO design and the AFO’s medical purpose was compiled. These metrics and constraints will establish the framework for designing a new AFO that carries out its medical purpose while also improving the user experience. The metrics can be categorized into several overarching areas for AFO improvement. Categories of user perspective related metrics include comfort, discreteness, aesthetics, ease of use, and compatibility with clothing. Categories of medical purpose related metrics include biomechanical functionality, durability, and affordability. These metrics were used to guide an iterative prototyping process. Six concepts were ideated and compared using system-level analysis. From these six concepts, two concepts – the piano wire model and the segmented model – were selected to move forward into prototyping. Evaluation of non-functional prototypes of the piano wire and segmented models determined that the piano wire model better fulfilled the metrics by offering increased stability, longer durability, fewer points for failure, and a strong enough core component to allow a sock to cover over the AFO while maintaining the overall structure. As such, the piano wire AFO has moved forward into the functional prototyping phase, and healthy subject testing is being designed and recruited to conduct design validation and verification.

Keywords: ankle-foot orthotic, assistive technology, human centered design, medical devices

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Authors: Genevieve Jorolan-Quintero

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The recording as well as the preservation of indigenous literature is an important task as it deals with a significant heritage of pre-colonial culture. The beliefs and traditions of a people are reflected in their oral narratives, such as the folk epic, which must be written down to insure their preservation. The epic poem for instance, known as dawot among the Mandaya, one of the indigenous communities in the southern region of the Philippines, narrates the customs, the ways of life, and the adventures of an ancient people. Nabayra, an expert on Philippine folkloric studies, stresses that still extant after centuries of unknown origin, the dawot was handed down to the magdadawot (bard) by word of mouth, forming the greatest bulk of Mandaya oral tradition. Unhampered by modern means of communication to distract her/him, the magdadawot has a sharp memory of the intricacies of the ancient art of chanting the panayday (verses) of the epic poem. The dawot has several hullubaton (episodes), each of which takes several nights to chant . The language used in these oral traditions is archaic Mandaya, no longer spoken or clearly understood by the present generation. There is urgency to the task of recording and writing down what remain of the epic poem since the singers and storytellers who have retained the memory and the skill of chanting and narrating the dawot and other forms of oral tradition in their original forms are getting fewer. The few who are gifted and skilled to transmit these ancient arts and wisdom are old and dying. Unlike the other Philippine epics (i.e. the Darangen, the Ulahingan, the Hinilawod, etc.), the Mandaya epic is yet to be recognized and given its rightful place among the recorded epics in Philippine Folk Literature. The general aim of this study was to put together and preserve an intangible heritage, the Mandaya hullubaton (episodes of the dawot), in order to preserve and promote appreciation for the oral traditions and cultural legacy of the Mandaya. It was able to record, transcribe, and translate four hullubaton of the folk epic into two languages, Visayan and English to insure understanding of their contents and significance among non-Mandaya audiences. Evident in the contents of the episodes are the cultural practices, ideals, life values, and traditions of the ancient Mandaya. While the conquests and adventures of the Mandaya heroes Lumungtad, Dilam, and Gambong highlight heroic virtues, the role of the Mandaya matriarch in family affairs is likewise stressed. The recording and the translation of the hullubaton and the dawot into commonly spoken languages will not only promote knowledge and understanding about their culture, but will also stimulate in the members of this cultural community a sense of pride for their literature and culture. Knowledge about indigenous cultural system and philosophy derived from their oral literature will serve as a springboard to further comparative researches dealing with indigenous mores and belief systems among the different tribes in the Philippines, in Asia, in Africa, and other countries in the world.

Keywords: Dawot, epic poem, Mandaya, Philippine folk literature

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Authors: Almudena Espin Perez, Tyler Risom, Carl Pelz, Isabel English, Robert M. Angelo, Rosalie Sears, Andrew J. Gentles

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Pancreatic ductal adenocarcinoma (PDAC) is one of the most deadly malignancies. The role of the tumor microenvironment (TME) is gaining significant attention in cancer research. Despite ongoing efforts, the nature of the interactions between tumors, immune cells, and stromal cells remains poorly understood. The cell-intrinsic properties that govern cell lineage plasticity in PDAC and extrinsic influences of immune populations require technically challenging approaches due to the inherently heterogeneous nature of PDAC. Understanding the cell lineage plasticity of PDAC will improve the development of novel strategies that could be translated to the clinic. Members of the team have demonstrated that the acquisition of ductal to neuroendocrine lineage plasticity in PDAC confers therapeutic resistance and is a biomarker of poor outcomes in patients. Our approach combines computational methods for deconvolving bulk transcriptomic cancer data using CIBERSORTx and high-throughput single-cell imaging using Multiplexed Ion Beam Imaging (MIBI) to study lineage plasticity in PDAC and its relationship to the infiltrating immune system. The CIBERSORTx algorithm uses signature matrices from immune cells and stroma from sorted and single-cell data in order to 1) infer the fractions of different immune cell types and stromal cells in bulked gene expression data and 2) impute a representative transcriptome profile for each cell type. We studied a unique set of 300 genomically well-characterized primary PDAC samples with rich clinical annotation. We deconvolved the PDAC transcriptome profiles using CIBERSORTx, leveraging publicly available single-cell RNA-seq data from normal pancreatic tissue and PDAC to estimate cell type proportions in PDAC, and digitally reconstruct cell-specific transcriptional profiles from our study dataset. We built signature matrices and optimized by simulations and comparison to ground truth data. We identified cell-type-specific transcriptional programs that contribute to cancer cell lineage plasticity, especially in the ductal compartment. We also studied cell differentiation hierarchies using CytoTRACE and predict cell lineage trajectories for acinar and ductal cells that we believe are pinpointing relevant information on PDAC progression. Collaborators (Angelo lab, Stanford University) has led the development of the Multiplexed Ion Beam Imaging (MIBI) platform for spatial proteomics. We will use in the very near future MIBI from tissue microarray of 40 PDAC samples to understand the spatial relationship between cancer cell lineage plasticity and stromal cells focused on infiltrating immune cells, using the relevant markers of PDAC plasticity identified from the RNA-seq analysis.

Keywords: deconvolution, imaging, microenvironment, PDAC

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