Search results for: boron nitride nanotube

Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

Abstract:

Solid-state lithium metal batteries (SSLMBs) are considered promising candidates for next-generation energy storage devices due to their superior energy density and excellent safety. However, recent findings have shown that the formation of lithium (Li) dendrites in SSLMBs still exhibits a terrible growth ability, which makes the development of SSLMBs have to face the challenges posed by the Li dendrite problem. In this work, an inorganic/organic mixture coating material (g-C3N4/ZIF-8/PVDF) was used to modify the surface of lithium metal anode (LMA). Then the modified LMA (denoted as g-C₃N₄@Li) was assembled with lithium nafion (LiNf) coated commercial NCM811 (LiNf@NCM811) using a bilayer hybrid solid electrolyte (Bi-HSE) that incorporated 20 wt.% (vs. polymer) LiNf coated Li6.05Ga0.25La3Zr2O11.8F0.2 ([email protected]) filler faced to the positive electrode and the other layer with 80 wt.% (vs. polymer) filler content faced to the g-C₃N₄@Li. The garnet-type Li6.05Ga0.25La3Zr2O11.8F0.2 (LG0.25LZOF) solid electrolyte was prepared via co-precipitation reaction process from Taylor flow reactor and modified using lithium nafion (LiNf), a Li-ion conducting polymer. The Bi-HSE exhibited high ionic conductivity of 6.8  10–4 S cm–1 at room temperature, and a wide electrochemical window (0–5.0 V vs. Li/Li+). The coin cell was charged between 2.8 to 4.5 V at 0.2C and delivered an initial specific discharge capacity of 194.3 mAh g–1 and after 100 cycles it maintained 81.8% of its initial capacity at room temperature. The presence of a nano-sheet g-C3N4/ZIF-8/PVDF as a composite coating material on the LMA surface suppress the dendrite growth and enhance the compatibility as well as the interfacial contact between anode/electrolyte membrane. The g-C3N4@Li symmetrical cells incorporating this hybrid electrolyte possessed excellent interfacial stability over 1000 h at 0.1 mA cm–2 and a high critical current density (1 mA cm–2). Moreover, the in-situ formation of Li3N on the solid electrolyte interface (SEI) layer as depicted from the XPS result also improves the ionic conductivity and interface contact during the charge/discharge process. Therefore, these novel multi-layered fabrication strategies of hybrid/composite solid electrolyte membranes and modification of the LMA surface using mixed coating materials have potential applications in the preparation of highly safe high-voltage cathodes for SSLMBs.

Keywords: high-voltage cathodes, hybrid solid electrolytes, garnet, graphitic-carbon nitride (g-C3N4), ZIF-8 MOF

Procedia PDF Downloads 67

Authors: W. Kritsarikan, T. Patcharawit, T. Yingnakorn, S. Khumkoa

Abstract:

Neodymium-iron-boron (NdFeB) magnets classified as high-power magnets are widely used in various applications such as electrical and medical devices and account for 13.5 % of the permanent magnet’s market. Since its typical composition of 29 - 32 % Nd, 64.2 – 68.5 % Fe and 1 – 1.2 % B contains a significant amount of rare earth metals and will be subjected to shortages in the future. Domestic NdFeB magnet waste recycling should therefore be developed in order to reduce social, environmental impacts toward a circular economy. Most research works focus on recycling the magnet wastes, both from the manufacturing process and end of life. Each type of wastes has different characteristics and compositions. As a result, these directly affect recycling efficiency as well as the types and purity of the recyclable products. This research, therefore, focused on the recycling of manufacturing NdFeB magnet waste obtained from the sintering stage of magnet production and the waste contained 23.6% Nd, 60.3% Fe and 0.261% B in order to recover high purity neodymium oxide (Nd₂O₃) using hybrid metallurgical process via oxidative roasting and selective leaching techniques. The sintered NdFeB waste was first ground to under 70 mesh prior to oxidative roasting at 550 - 800 °C to enable selective leaching of neodymium in the subsequent leaching step using H₂SO₄ at 2.5 M over 24 h. The leachate was then subjected to drying and roasting at 700 – 800 °C prior to precipitation by oxalic acid and calcination to obtain neodymium oxide as the recycling product. According to XRD analyses, it was found that increasing oxidative roasting temperature led to an increasing amount of hematite (Fe₂O₃) as the main composition with a smaller amount of magnetite (Fe₃O₄) found. Peaks of neodymium oxide (Nd₂O₃) were also observed in a lesser amount. Furthermore, neodymium iron oxide (NdFeO₃) was present and its XRD peaks were pronounced at higher oxidative roasting temperatures. When proceeded to acid leaching and drying, iron sulfate and neodymium sulfate were mainly obtained. After the roasting step prior to water leaching, iron sulfate was converted to form hematite as the main compound, while neodymium sulfate remained in the ingredient. However, a small amount of magnetite was still detected by XRD. The higher roasting temperature at 800 °C resulted in a greater Fe₂O₃ to Nd₂(SO₄)₃ ratio, indicating a more effective roasting temperature. Iron oxides were subsequently water leached and filtered out while the solution contained mainly neodymium sulfate. Therefore, low oxidative roasting temperature not exceeding 600 °C followed by acid leaching and roasting at 800 °C gave the optimum condition for further steps of precipitation and calcination to finally achieve neodymium oxide.

Keywords: NdFeB magnet waste, oxidative roasting, recycling, selective leaching

Procedia PDF Downloads 182

Authors: Lekgowa Collen Makola, Cecil Naphtaly Moro Ouma, Sharon Moeno, Langelihle Dlamini

Abstract:

In recent years, advancement in the field of nanotechnology has evolved new strategies to address energy and environmental issues. Amongst the developing technologies, visible-light-driven photocatalysis is regarded as a sustainable approach for energy production and environmental detoxifications, where transition metal oxides (TMOs) and metal-free carbon-based semiconductors such as graphitic carbon nitride (CN) evidenced notable potential in this matter. Herein, g-C₃N₄@WO₃@Ti₃C₂Tx three-component multijunction photocatalyst was fabricated via facile ultrasonic-assisted self-assembly, followed by calcination to facilitate extensive integrations of the materials. A series of different Ti₃C₂ wt% loading in the g-C₃N4@WO₃@Ti₃C₂Tx were prepared and represented as 1-CWT, 3-CWT, 5-CWT, and 7-CWT corresponding to 1, 3, 5, and 7wt%, respectively. Systematic characterization using spectroscopic and microscopic techniques were employed to validate the successful preparation of the photocatalysts. Enhanced optoelectronic and photoelectrochemical properties were observed for the WO₃@Ti₃C2@g-C₃N4 heterostructure with respect to the individual materials. Photoluminescence spectra and Nyquist plots show restrained recombination rates and improved photocarrier conductivities, respectively, and this was credited to the synergistic coupling effect and the presence of highly conductive Ti₃C2 MXene. The strong interfacial contact surfaces upon the formation of the composite were confirmed using XPS. Multiple charge transfer mechanisms were proposed for the WO3@Ti3C₂@g-C3N4, which couples Z-scheme and Schottky-junction mediated with Ti3C2 MXene. Bode phase plots show improved charge carrier life-times upon the formation of the multijunctional photocatalyst. Moreover, transient photocurrent density of 7-CWT is 40 and seven (7) times higher compared to that of g-C₃N4 and WO3, correspondingly. Unlike in the traditional Z-Scheme, the formed ternary heterostructure possesses interfaces through the metallic 2D Ti₃C₂ MXene, which provided charge transfer channels for efficient photocarrier transfers with carrier concentrations (ND) of 17.49×1021 cm-3 and 4.86% photo-to-chemical conversion efficiency. The as-prepared ternary g-C₃N₄@WO₃@Ti₃C₂Tx exhibited excellent photoelectrochemical properties with reserved redox band potential potencies to facilitate efficient photo-oxidation and -reduction reactions. The fabricated multijunction photocatalyst exhibits potentials to be used in an extensive range of photocatalytic process vis., production of valuable hydrocarbons from CO₂, production of H₂, and degradation of a plethora of pollutants from wastewater.

Keywords: photocatalysis, Z-scheme, multijunction heterostructure, Ti₃C₂ MXene, g-C₃N₄

Procedia PDF Downloads 123

Authors: Heming Yao

Abstract:

Graphene-based percolative strain gauges could find applications in many places such as touch panels, artificial skins or human motion detection because of its advantages over conventional strain gauges such as flexibility and transparency. These strain gauges rely on a novel sensing mechanism that depends on strain-induced morphology changes. Once a compression or tension strain is applied to Graphene-based percolative strain gauges, the overlap area between neighboring flakes becomes smaller or larger, which is reflected by the considerable change of resistance. Tiny strain change on graphene-based percolative strain sensor can act as an important leverage to tremendously increase resistance of strain sensor, which equipped graphene-based percolative strain gauges with higher gauge factor. Despite ongoing research in the underlying sensing mechanism and the limits of sensitivity, neither suitable understanding has been obtained of what intrinsic factors play the key role in adjust gauge factor, nor explanation on how the strain gauge sensitivity can be enhanced, which is undoubtedly considerably meaningful and provides guideline to design novel and easy-produced strain sensor with high gauge factor. We here simulated the strain process by modeling graphene flakes and its percolative networks. We constructed the 3D resistance network by simulating overlapping process of graphene flakes and interconnecting tremendous number of resistance elements which were obtained by fractionizing each piece of graphene. With strain increasing, the overlapping graphenes was dislocated on new stretched simulation graphene flake simulation film and a new simulation resistance network was formed with smaller flake number density. By solving the resistance network, we can get the resistance of simulation film under different strain. Furthermore, by simulation on possible variable parameters, such as out-of-plane resistance, in-plane resistance, flake size, we obtained the changing tendency of gauge factor with all these variable parameters. Compared with the experimental data, we verified the feasibility of our model and analysis. The increase of out-of-plane resistance of graphene flake and the initial resistance of sensor, based on flake network, both improved gauge factor of sensor, while the smaller graphene flake size gave greater gauge factor. This work can not only serve as a guideline to improve the sensitivity and applicability of graphene-based strain sensors in the future, but also provides method to find the limitation of gauge factor for strain sensor based on graphene flake. Besides, our method can be easily transferred to predict gauge factor of strain sensor based on other nano-structured transparent optical conductors, such as nanowire and carbon nanotube, or of their hybrid with graphene flakes.

Keywords: graphene, gauge factor, percolative transport, strain sensor

Procedia PDF Downloads 416

Authors: Lucas Barbosa Da Silva, Jun Okamoto Jr.

Abstract:

Precision Agriculture has long being benefited from crop fields’ aerial imagery. This important tool has allowed identifying patterns in crop fields, generating useful information to the production management. Reflectance intensity data in different ranges from the electromagnetic spectrum may indicate presence or absence of nutrients in the soil of an area. Different relations between the different light bands may generate even more detailed information. The knowledge of the nutrients content in the soil or in the crop during its growth is a valuable asset to the farmer that seeks to optimize its yield. However, small farmers in Brazil often lack the resources to access this kind information, and, even when they do, it is not presented in a comprehensive and/or objective way. So, the challenges of implementing this technology ranges from the sampling of the imagery, using aerial platforms, building of a mosaic with the images to cover the entire crop field, extracting the reflectance information from it and analyzing its relationship with the parameters of interest, to the display of the results in a manner that the farmer may take the necessary decisions more objectively. In this work, it’s proposed an analysis of soil nutrient contents based on image processing of satellite imagery and comparing its outtakes with commercial laboratory’s chemical analysis. Also, sources of satellite imagery are compared, to assess the feasibility of using Google Earth data in this application, and the impacts of doing so, versus the application of imagery from satellites like Landsat-8 and Pleiades. Furthermore, an algorithm for building mosaics is implemented using Google Earth imagery and finally, the possibility of using unmanned aerial vehicles is analyzed. From the data obtained, some soil parameters are estimated, namely, the content of Potassium, Phosphorus, Boron, Manganese, among others. The suitability of Google Earth Imagery for this application is verified within a reasonable margin, when compared to Pleiades Satellite imagery and to the current commercial model. It is also verified that the mosaic construction method has little or no influence on the estimation results. Variability maps are created over the covered area and the impacts of the image resolution and sample time frame are discussed, allowing easy assessments of the results. The final results show that easy and cheaper remote sensing and analysis methods are possible and feasible alternatives for the small farmer, with little access to technological and/or financial resources, to make more accurate decisions about soil nutrient management.

Keywords: remote sensing, precision agriculture, mosaic, soil, nutrient content, satellite imagery, aerial imagery

Procedia PDF Downloads 175

Authors: Amit Bhunia, Mohit Kumar Singh, Maryam Al Huwayz, Mohamed Henini, Shouvik Datta

Abstract:

We report [https://arxiv.org/abs/2107.13518] experimental detection and control of Schrodinger’s Cat like macroscopically large, quantum coherent state of a two-component Bose-Einstein condensate of spatially indirect electron-hole pairs or excitons using a resonant tunneling diode of III-V Semiconductors. This provides access to millions of excitons as qubits to allow efficient, fault-tolerant quantum computation. In this work, we measure phase-coherent periodic oscillations in photo-generated capacitance as a function of an applied voltage bias and light intensity over a macroscopically large area. Periodic presence and absence of splitting of excitonic peaks in the optical spectra measured by photocapacitance point towards tunneling induced variations in capacitive coupling between the quantum well and quantum dots. Observation of negative ‘quantum capacitance’ due to a screening of charge carriers by the quantum well indicates Coulomb correlations of interacting excitons in the plane of the sample. We also establish that coherent resonant tunneling in this well-dot heterostructure restricts the available momentum space of the charge carriers within this quantum well. Consequently, the electric polarization vector of the associated indirect excitons collective orients along the direction of applied bias and these excitons undergo Bose-Einstein condensation below ~100 K. Generation of interference beats in photocapacitance oscillation even with incoherent white light further confirm the presence of stable, long-range spatial correlation among these indirect excitons. We finally demonstrate collective Rabi oscillations of these macroscopically large, ‘multipartite’, two-level, coupled and uncoupled quantum states of excitonic condensate as qubits. Therefore, our study not only brings the physics and technology of Bose-Einstein condensation within the reaches of semiconductor chips but also opens up experimental investigations of the fundamentals of quantum physics using similar techniques. Operational temperatures of such two-component excitonic BEC can be raised further with a more densely packed, ordered array of QDs and/or using materials having larger excitonic binding energies. However, fabrications of single crystals of 0D-2D heterostructures using 2D materials (e.g. transition metal di-chalcogenides, oxides, perovskites etc.) having higher excitonic binding energies are still an open challenge for semiconductor optoelectronics. As of now, these 0D-2D heterostructures can already be scaled up for mass production of miniaturized, portable quantum optoelectronic devices using the existing III-V and/or Nitride based semiconductor fabrication technologies.

Keywords: exciton, Bose-Einstein condensation, quantum computation, heterostructures, semiconductor Physics, quantum fluids, Schrodinger's Cat

Procedia PDF Downloads 180

Authors: Z. Terzopoulou, I. Koliakou, D. Bikiaris

Abstract:

Tissue engineering offers a new approach to regenerate diseased or damaged tissues such as bone. Great effort is devoted to eliminating the need of removing non-degradable implants at the end of their life span, with biodegradable polymers playing a major part. Poly(ε-caprolactone) (PCL) is one of the best candidates for this purpose due to its high permeability, good biodegradability and exceptional biocompatibility, which has stimulated extensive research into its potential application in the biomedical fields. However, PCL degrades much slower than other known biodegradable polymers and has a total degradation of 2-4 years depending on the initial molecular weight of the device. This is due to its relatively hydrophobic character and high crystallinity. Consequently, much attention has been given to the tunable degradation of PCL to meet the diverse requirements of biomedicine. Poly(ε-caprolactone) (PCL) is a biodegradable polyester that lacks bioactivity, so when used in bone tissue engineering, new bone tissue cannot bond tightly on the polymeric surface. Therefore, it is important to incorporate reinforcing fillers into PCL matrix in order to result in a promising combination of bioactivity, biodegradability, and strength. Natural clay halloysite nanotubes (HNTs) were incorporated into PCL polymeric matrix, via in situ ring-opening polymerization of caprolactone, in concentrations 0.5, 1 and 2.5 wt%. Both unmodified and modified with aminopropyltrimethoxysilane (APTES) HNTs were used in this study. The effect of nanofiller concentration and functionalization with end-amino groups on the physicochemical properties of the prepared nanocomposites was studied. Mechanical properties were found enhanced after the incorporation of nanofillers, while the modification increased further the values of tensile and impact strength. Thermal stability of PCL was not affected by the presence of nanofillers, while the crystallization rate that was studied by Differential Scanning Calorimetry (DSC) and Polarized Light Optical Microscopy (POM) increased. All materials were subjected to enzymatic hydrolysis in phosphate buffer in the presence of lipases. Due to the hydrophilic nature of HNTs, the biodegradation rate of nanocomposites was higher compared to neat PCL. In order to confirm the effect of hydrophilicity, contact angle measurements were also performed. In vitro biomineralization test confirmed that all samples were bioactive as mineral deposits were detected by X-ray diffractometry after incubation in SBF. All scaffolds were tested in relevant cell culture using osteoblast-like cells (MG-63) to demonstrate their biocompatibility

Keywords: biomaterials, nanocomposites, scaffolds, tissue engineering

Procedia PDF Downloads 316

Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

Abstract:

Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H₂) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H₂, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO Hydrodeoxygenation, DFT, liquid fuels, XPS, XTL

Procedia PDF Downloads 347

Authors: Pei-Ying Lo, Jing-Hao Ciou, Kai-Cheng Yang, Jia-Huei Zheng, Shih-Hsiang Huang, Kuen-Chan Lee, Er-Chieh Cho

Abstract:

As-produced CNTs are insoluble in all organic solvents and aqueous solutions have imposed limitations to the use of CNTs. Therefore, how to debundle carbon nanotubes and to modify them for further uses is an important issue. There are several methods for the dispersion of CNTs in water using covalent attachment of hydrophilic groups to the surface of tubes. These methods, however, alter the electronic structure of the nanotubes by disrupting the network of sp2 hybridized carbons. In order to keep the nanotubes’ intrinsic mechanical and electrical properties intact, non-covalent interactions are increasingly being explored as an alternative route for dispersion. Apart from conventional surfactants such as sodium dodecylsulfate (SDS) or sodium dodecylbenzenesulfonate (SDBS) which are highly effective in dispersing CNTs, biopolymers have received much attention as dispersing agents due to the anticipated biocompatibility of the dispersed CNTs. Also, The pyrenyl group is known to interact strongly with the basal plane of graphene via π-stacking. In this study, a highly re-dispersible biopolymer is reported for the synthesis of pyrene-modified poly-L-lysine (PBPL) and poly(D-Glu, D-Lys) (PGLP). To provide the evidence of the safety of the PBPL/CNT & PGLP/CNT materials we use in this study, H1299 and HCT116 cells were incubated with PBPL/CNT & PGLP/CNT materials for toxicity analysis, MTS assays. The results from MTS assays indicated that no significant cellular toxicity was shown in H1299 and HCT116 cells. Furthermore, the fluorescence marker fluorescein isothiocyanate (FITC) was added to PBPL & PGLP dispersions. From the fluorescent measurements showed that the chemical functionalisation of the PBPL/CNT & PGLP/CNT conjugates with the fluorescence marker were successful. The fluorescent PBPL/CNT & PGLP/CNT conjugates could find application in medical imaging. In the next step, the GFP gene is immobilized onto PBPL/CNT conjugates by introducing electrostatic interaction. GFP-transfected cells that emitted fluorescence were imaged and counted under a fluorescence microscope. Due to the unique biocompatibility of PBPL modified CNTs, the GFP gene could be transported into H1299 cells without using antibodies. The applicability of such soluble and chemically functionalised polypeptide/CNT conjugates in biomedicine is currently investigated. We expect that this polypeptide/CNT system will be a safe and multi-functional nanomedical delivery platform and contribute to future medical therapy.

Keywords: carbon nanotube, nanotoxicology, GFP transfection, polypeptide/CNT hybrids

Procedia PDF Downloads 339

Authors: Xuerui Niu, Bolin Wang, Xinchuang Zhang, Xiaohua Ma, Bin Hou, Ling Yang

Abstract:

The application of discrete GaN-based power switches requires the collaboration of silicon-based peripheral circuit structures. However, the packages and interconnection between the Si and GaN devices can introduce parasitic effects to the circuit, which has great impacts on GaN power transistors. GaN-based monolithic power integration technology is an emerging solution which can improve the stability of circuits and allow the GaN-based devices to achieve more functions. Complementary logic circuits consisting of GaN-based E-mode p-channel heterostructure field-effect transistors (p-HFETs) and E-mode n-channel HEMTs can be served as the gate drivers. E-mode p-HFETs with recessed gate have attracted increasing interest because of the low leakage current and large gate swing. However, they suffer from a poor interface between the gate dielectric and polarized nitride layers. The reliability of p-HFETs is analyzed and discussed in this work. In circuit applications, the inverter is always operated with dynamic gate voltage (VGS) rather than a constant VGS. Therefore, dynamic electrical stress has been simulated to resemble the operation conditions for E-mode p-HFETs. The dynamic electrical stress condition is as follows. VGS is a square waveform switching from -5 V to 0 V, VDS is fixed, and the source grounded. The frequency of the square waveform is 100kHz with the rising/falling time of 100 ns and duty ratio of 50%. The effective stress time is 1000s. A number of stress tests are carried out. The stress was briefly interrupted to measure the linear IDS-VGS, saturation IDS-VGS, As VGS switches from -5 V to 0 V and VDS = 0 V, devices are under negative-bias-instability (NBI) condition. Holes are trapped at the interface of oxide layer and GaN channel layer, which results in the reduction of VTH. The negative shift of VTH is serious at the first 10s and then changes slightly with the following stress time. However, different phenomenon is observed when VDS reduces to -5V. VTH shifts negatively during stress condition, and the variation in VTH increases with time, which is different from that when VDS is 0V. Two mechanisms exists in this condition. On the one hand, the electric field in the gate region is influenced by the drain voltage, so that the trapping behavior of holes in the gate region changes. The impact of the gate voltage is weakened. On the other hand, large drain voltage can induce the hot holes generation and lead to serious hot carrier stress (HCS) degradation with time. The poor-quality interface between the oxide layer and GaN channel layer at the gate region makes a major contribution to the high-density interface traps, which will greatly influence the reliability of devices. These results emphasize that the improved etching and pretreatment processes needs to be developed so that high-performance GaN complementary logics with enhanced stability can be achieved.

Keywords: GaN-based E-mode p-HFETs, dynamic electric stress, threshold voltage, monolithic power integration technology

Procedia PDF Downloads 92

Authors: Esther Van Andel, Stefanie C. Lange, Maarten M. J. Smulders, Han Zuilhof

Abstract:

False outcomes of diagnostic tests are a major concern in medical health care. To improve the reliability of surface-based diagnostic tests, it is of crucial importance to diminish background signals that arise from the non-specific binding of biomolecules, a process called fouling. The aim is to create surfaces that repel all biomolecules except the molecule of interest. This can be achieved by incorporating antifouling protein repellent coatings in between the sensor surface and it’s recognition elements (e.g. antibodies, sugars, aptamers). Zwitterionic polymer brushes are considered excellent antifouling materials, however, to be able to bind the molecule of interest, the polymer brushes have to be functionalized and so far this was only achieved at the expense of either antifouling or binding capacity. To overcome this limitation, we combined both features into one single monomer: a zwitterionic sulfobetaine, ensuring antifouling capabilities, equipped with a clickable azide moiety which allows for further functionalization. By copolymerizing this monomer together with a standard sulfobetaine, the number of azides (and with that the number of recognition elements) can be tuned depending on the application. First, the clickable azido-monomer was synthesized and characterized, followed by copolymerizing this monomer to yield functionalizable antifouling brushes. The brushes were fully characterized using surface characterization techniques like XPS, contact angle measurements, G-ATR-FTIR and XRR. As a proof of principle, the brushes were subsequently functionalized with biotin via strain-promoted alkyne azide click reactions, which yielded a fully zwitterionic biotin-containing 3D-functionalized coating. The sensing capacity was evaluated by reflectometry using avidin and fibrinogen containing protein solutions. The surfaces showed excellent antifouling properties as illustrated by the complete absence of non-specific fibrinogen binding, while at the same time clear responses were seen for the specific binding of avidin. A great increase in signal-to-noise ratio was observed, even when the amount of functional groups was lowered to 1%, compared to traditional modification of sulfobetaine brushes that rely on a 2D-approach in which only the top-layer can be functionalized. This study was performed on stoichiometric silicon nitride surfaces for future microring resonator based assays, however, this methodology can be transferred to other biosensor platforms which are currently being investigated. The approach presented herein enables a highly efficient strategy for selective binding with retained antifouling properties for improved signal-to-noise ratios in binding assays. The number of recognition units can be adjusted to a specific need, e.g. depending on the size of the analyte to be bound, widening the scope of these functionalizable surface coatings.

Keywords: antifouling, signal-to-noise ratio, surface functionalization, zwitterionic polymer brushes

Procedia PDF Downloads 306

Authors: Bastien Sanglard, Simon Cayez, Guillaume Viau, Thomas Blon, Julian Carrey, Sébastien Lachaize

Abstract:

The need to develop clean production processes is a key challenge of any industry. Steel and iron industries are particularly concerned since they emit 6.8% of global anthropogenic greenhouse gas emissions. One key step of the process is the high-temperature reduction of iron ore using coke, leading to large amounts of CO2 emissions. One route to decrease impacts is to get rid of fossil fuels by changing both the heat source and the reducer. The present work aims at investigating experimentally the possibility to use concentrated solar energy and carbon-free reducing agents. Two sets of experimentations were realized. First, in situ X-ray diffraction on pure and industrial powder of hematite was realized to study the phase evolution as a function of temperature during reduction under hydrogen and ammonia. Secondly, experiments were performed on industrial iron ore pellets, which were reduced by NH3 or H2 into a “solar furnace” composed of a controllable 1600W Xenon lamp to simulate and control the solar concentrated irradiation of a glass reactor and of a diaphragm to control light flux. Temperature and pressure were recorded during each experiment via thermocouples and pressure sensors. The percentage of iron oxide converted to iron (called thereafter “reduction ratio”) was found through Rietveld refinement. The power of the light source and the reduction time were varied. Results obtained in the diffractometer reaction chamber show that iron begins to form at 300°C with pure Fe2O3 powder and 400°C with industrial iron ore when maintained at this temperature for 60 minutes and 80 minutes, respectively. Magnetite and wuestite are detected on both powders during the reduction under hydrogen; under ammonia, iron nitride is also detected for temperatures between400°C and 600°C. All the iron oxide was converted to iron for a reaction of 60 min at 500°C, whereas a conversion ratio of 96% was reached with industrial powder for a reaction of 240 min at 600°C under hydrogen. Under ammonia, full conversion was also reached after 240 min of reduction at 600 °C. For experimentations into the solar furnace with iron ore pellets, the lamp power and the shutter opening were varied. An 83.2% conversion ratio was obtained with a light power of 67 W/cm2 without turning over the pellets. Nevertheless, under the same conditions, turning over the pellets in the middle of the experiment permits to reach a conversion ratio of 86.4%. A reduction ratio of 95% was reached with an exposure of 16 min by turning over pellets at half time with a flux of 169W/cm2. Similar or slightly better results were obtained under an ammonia reducing atmosphere. Under the same flux, the highest reduction yield of 97.3% was obtained under ammonia after 28 minutes of exposure. The chemical reaction itself, including the solar heat source, does not produce any greenhouse gases, so solar metallurgy represents a serious way to reduce greenhouse gas emission of metallurgy industry. Nevertheless, the ecological impact of the reducers must be investigated, which will be done in future work.

Keywords: solar concentration, metallurgy, ammonia, hydrogen, sustainability

Procedia PDF Downloads 138

Authors: Farzan Gity, Lida Ansari, Ian M. Povey, Roger E. Nagle, James C. Greer

Abstract:

Titanium nitride (TiN) films have been widely used in variety of fields, due to its unique electrical, chemical, physical and mechanical properties, including low electrical resistivity, chemical stability, and high thermal conductivity. In microelectronic devices, thin continuous TiN films are commonly used as diffusion barrier and metal gate material. However, as the film thickness decreases below a few nanometers, electrical properties of the film alter considerably. In this study, the physical and electrical characteristics of 1.5nm to 22nm thin films deposited by Plasma-Enhanced Atomic Layer Deposition (PE-ALD) using Tetrakis(dimethylamino)titanium(IV), (TDMAT) chemistry and Ar/N2 plasma on 80nm SiO2 capped in-situ by 2nm Al2O3 are investigated. ALD technique allows uniformly-thick films at monolayer level in a highly controlled manner. The chemistry incorporates low level of oxygen into the TiN films forming titanium oxynitride (TiON). Thickness of the films is characterized by Transmission Electron Microscopy (TEM) which confirms the uniformity of the films. Surface morphology of the films is investigated by Atomic Force Microscopy (AFM) indicating sub-nanometer surface roughness. Hall measurements are performed to determine the parameters such as carrier mobility, type and concentration, as well as resistivity. The >5nm-thick films exhibit metallic behavior; however, we have observed that thin film resistivity is modulated significantly by film thickness such that there are more than 5 orders of magnitude increment in the sheet resistance at room temperature when comparing 5nm and 1.5nm films. Scattering effects at interfaces and grain boundaries could play a role in thickness-dependent resistivity in addition to quantum confinement effect that could occur at ultra-thin films: based on our measurements the carrier concentration is decreased from 1.5E22 1/cm3 to 5.5E17 1/cm3, while the mobility is increased from < 0.1 cm2/V.s to ~4 cm2/V.s for the 5nm and 1.5nm films, respectively. Also, measurements at different temperatures indicate that the resistivity is relatively constant for the 5nm film, while for the 1.5nm film more than 2 orders of magnitude reduction has been observed over the range of 220K to 400K. The activation energy of the 2.5nm and 1.5nm films is 30meV and 125meV, respectively, indicating that the TiON ultra-thin films are exhibiting semiconducting behaviour attributing this effect to a metal-semiconductor transition. By the same token, the contact is no longer Ohmic for the thinnest film (i.e., 1.5nm-thick film); hence, a modified lift-off process was developed to selectively deposit thicker films allowing us to perform electrical measurements with low contact resistance on the raised contact regions. Our atomic scale simulations based on molecular dynamic-generated amorphous TiON structures with low oxygen content confirm our experimental observations indicating highly n-type thin films.

Keywords: activation energy, ALD, metal-semiconductor transition, resistivity, titanium oxynitride, ultra-thin film

Procedia PDF Downloads 292

Authors: T. Kuchukhidze, N. Jalagonia, T. Archuadze, G. Bokuchava

Abstract:

The growing scientific-technological progress in modern civilization causes actuality of producing construction materials which can successfully work in conditions of high temperature, radiation, pressure, speed, and chemically aggressive environment. Such extreme conditions can withstand very few types of materials and among them, ceramic materials are in the first place. Corundum ceramics is the most useful material for creation of constructive nodes and products of various purposes for its low cost, easy accessibility to raw materials and good combination of physical-chemical properties. However, ceramic composite materials have one disadvantage; they are less plastics and have lower toughness. In order to increase the plasticity, the ceramics are reinforced by various dopants, that reduces the growth of the cracks. It is shown, that adding of even small amount of carbon fibers and carbon nanotubes (CNT) as reinforcing material significantly improves mechanical properties of the products, keeping at the same time advantages of alundum ceramics. Graphene in composite material acts in the same way as inorganic dopants (MgO, ZrO2, SiC and others) and performs the role of aluminum oxide inhibitor, as it creates shell, that gives possibility to reduce sintering temperature and at the same time it acts as damper, because scattering of a shock wave takes place on carbon structures. Application of different structural modification of carbon (graphene, nanotube and others) as reinforced material, gives possibility to create multi-purpose highly requested composite materials based on alundum ceramics. In the present work offers simplified technology for obtaining of aluminum oxide ceramics, reinforced with carbon nanostructures, during which chemical modification with doping carbon nanostructures will be implemented in the process of synthesis of final powdery composite – Alumina. In charge doping carbon nanostructures connected to matrix substance with C-O-Al bonds, that provide their homogeneous spatial distribution. In ceramic obtained as a result of consolidation of such powders carbon fragments equally distributed in the entire matrix of aluminum oxide, that cause increase of bending strength and crack-resistance. The proposed way to prepare the charge simplifies the technological process, decreases energy consumption, synthesis duration and therefore requires less financial expenses. In the implementation of this work, modern instrumental methods were used: electronic and optical microscopy, X-ray structural and granulometric analysis, UV, IR, and Raman spectroscopy.

Keywords: ceramic materials, α-Al₂O₃, carbon nanostructures, composites, characterization, hot-pressing

Procedia PDF Downloads 119

Authors: Daniela Ailincai, Bogdan C. Simionescu, Luminita Marin

Abstract:

Polymer dispersed liquid crystals (PDLC) represent an interesting class of materials which combine the ability of polymers to form films and their mechanical strength with the opto-electronic properties of liquid crystals. The proper choice of the two components - the liquid crystal and the polymeric matrix - leads to materials suitable for a large area of applications, from electronics to biomedical devices. The objective of our work was to obtain PDLC films with potential applications in the biomedical field, using poly vinyl alcohol boric acid (PVAB) as a polymeric matrix for the first time. Presenting all the tremendous properties of poly vinyl alcohol (such as: biocompatibility, biodegradability, water solubility, good chemical stability and film forming ability), PVAB brings the advantage of containing the electron deficient boron atom, and due to this, it should promote the liquid crystal anchoring and a narrow liquid crystal droplets polydispersity. Two different PDLC systems have been obtained, by the use of two liquid crystals, a nematic commercial one: 4-cyano-4’-penthylbiphenyl (5CB) and a new smectic liquid crystal, synthesized by us: buthyl-p-[p’-n-octyloxy benzoyloxy] benzoate (BBO). The PDLC composites have been obtained by the encapsulation method, working with four different ratios between the polymeric matrix and the liquid crystal, from 60:40 to 90:10. In all cases, the composites were able to form free standing, flexible films. Polarized light microscopy, scanning electron microscopy, differential scanning calorimetry, RAMAN- spectroscopy and the contact angle measurements have been performed, in order to characterize the new composites. The new smectic liquid crystal has been characterized using 1H-NMR and single crystal X-ray diffraction and its thermotropic behavior has been established using differential scanning calorimetry and polarized light microscopy. The polarized light microscopy evidenced the formation of round birefringent droplets, anchored homeotropic in the first case and planar in the second, with a narrow dimensional polydispersity, especially for the PDLC containing the largest amount of liquid crystal, fact evidenced by SEM, also. The obtained values for the water to air contact angle showed that the composites have a proper hydrophilic-hydrophobic balance, making them potential candidates for bioapplications. More than this, our studies demonstrated that the water to air contact angle varies as a function of PVAB matrix crystalinity degree, which can be controled as a function of time. This fact allowed us to conclude that the use of PVAB as matrix for PDLCs obtaining offers the possibility to modulate their properties for specific applications.

Keywords: 4-cyano-4’-penthylbiphenyl, buthyl-p-[p’-n-octyloxy benzoyloxy] benzoate, contact angle, polymer dispersed liquid crystals, poly vinyl alcohol boric acid

Procedia PDF Downloads 450

Authors: R. R. Galiev, I. I. Lykov, A. E. Shitikov, I. A. Bilenko

Abstract:

Dual-comb interferometry is based on the mixing of two optical frequency combs with slightly different lines spacing which results in the mapping of the optical spectrum into the radio-frequency domain for future digitizing and numerical processing. The dual-comb approach enables diverse applications, including metrology, fast high-precision spectroscopy, and distance range. Ordinary frequency-modulated continuous-wave (FMCW) laser-based Light Identification Detection and Ranging systems (LIDARs) suffer from two main disadvantages: slow and unreliable mechanical, spatial scan and a rather wide linewidth of conventional lasers, which limits speed measurement resolution. Dual-comb distance measurements with Allan deviations down to 12 nanometers at averaging times of 13 microseconds, along with ultrafast ranging at acquisition rates of 100 megahertz, allowing for an in-flight sampling of gun projectiles moving at 150 meters per second, was previously demonstrated. Nevertheless, pump lasers with EDFA amplifiers made the device bulky and expensive. An alternative approach is a direct coupling of the laser to a reference microring cavity. Backscattering can tune the laser to the eigenfrequency of the cavity via the so-called self-injection locked (SIL) effect. Moreover, the nonlinearity of the cavity allows a solitonic frequency comb generation in the very same cavity. In this work, we developed a fully integrated, power-efficient, electrically driven dual-micro comb source based on the semiconductor lasers SIL to high-quality integrated Si3N4 microresonators. We managed to obtain robust 1400-1700 nm combs generation with a 150 GHz or 1 THz lines spacing and measure less than a 1 kHz Lorentzian withs of stable, MHz spaced beat notes in a GHz band using two separated chips, each pumped by its own, self-injection locked laser. A deep investigation of the SIL dynamic allows us to find out the turn-key operation regime even for affordable Fabry-Perot multifrequency lasers used as a pump. It is important that such lasers are usually more powerful than DFB ones, which were also tested in our experiments. In order to test the advantages of the proposed techniques, we experimentally measured a minimum detectable speed of a reflective object. It has been shown that the narrow line of the laser locked to the microresonator provides markedly better velocity accuracy, showing velocity resolution down to 16 nm/s, while the no-SIL diode laser only allowed 160 nm/s with good accuracy. The results obtained are in agreement with the estimations and open up ways to develop LIDARs based on compact and cheap lasers. Our implementation uses affordable components, including semiconductor laser diodes and commercially available silicon nitride photonic circuits with microresonators.

Keywords: dual-comb spectroscopy, LIDAR, optical microresonator, self-injection locking

Procedia PDF Downloads 72

Authors: Deb Kumar Shah, M. Shaheer Akhtar, Ha Ryeon Lee, O-Bong Yang, Chong Yeal Kim

Abstract:

The crystalline silicon (Si) solar cells are highly renowned photovoltaic technology and well-established as the commercial solar technology. Most of the solar panels are globally installed with the crystalline Si solar modules. At the present scenario, the major photovoltaic (PV) market is shared by c-Si solar cells, but the cost of c-Si panels are still very high as compared with the other PV technology. In order to reduce the cost of Si solar panels, few necessary steps such as low-cost Si manufacturing, cheap antireflection coating materials, inexpensive solar panel manufacturing are to be considered. It is known that the antireflection (AR) layer in c-Si solar cell is an important component to reduce Fresnel reflection for improving the overall conversion efficiency. Generally, Si wafer exhibits the 30% reflection because it normally poses the two major intrinsic drawbacks such as; the spectral mismatch loss and the high Fresnel reflection loss due to the high contrast of refractive indices between air and silicon wafer. In recent years, researchers and scientists are highly devoted to a lot of researches in the field of searching effective and low-cost AR materials. Silicon nitride (SiNx) is well-known AR materials in commercial c-Si solar cells due to its good deposition and interaction with passivated Si surfaces. However, the deposition of SiNx AR is usually performed by expensive plasma enhanced chemical vapor deposition (PECVD) process which could have several demerits like difficult handling and damaging the Si substrate by plasma when secondary electrons collide with the wafer surface for AR coating. It is very important to explore new, low cost and effective AR deposition process to cut the manufacturing cost of c-Si solar cells. One can also be realized that a nano-texturing process like the growth of nanowires, nanorods, nanopyramids, nanopillars, etc. on Si wafer can provide a low reflection on the surface of Si wafer based solar cells. The above nanostructures might be enhanced the antireflection property which provides the larger surface area and effective light trapping. In this work, we report on the development of crystalline Si solar cells without using the AR layer. The Silicon wafer was modified by growing nanowires like Si nanostructures using the wet controlled etching method and directly used for the fabrication of Si solar cell without AR. The nanostructures over Si wafer were optimized in terms of sizes, lengths, and densities by changing the etching conditions. Well-defined and aligned wires like structures were achieved when the etching time is 20 to 30 min. The prepared Si nanostructured displayed the minimum reflectance ~1.64% at 850 nm with the average reflectance of ~2.25% in the wavelength range from 400-1000 nm. The nanostructured Si wafer based solar cells achieved the comparable power conversion efficiency in comparison with c-Si solar cells with SiNx AR layer. From this study, it is confirmed that the reported method (controlled wet etching) is an easy, facile method for preparation of nanostructured like wires on Si wafer with low reflectance in the whole visible region, which has greater prospects in developing c-Si solar cells without AR layer at low cost.

Keywords: chemical etching, conversion efficiency, silicon nanostructures, silicon solar cells, surface modification

Procedia PDF Downloads 125

Authors: Anna Kolanowska, Anna Kuziel, Sławomir Boncel

Abstract:

Carbon nanotubes (CNTs) represent a combination of lightness and nanoscopic size with high tensile strength, excellent thermal and electrical conductivity. By now, CNTs have been used as a support in heterogeneous catalysis (CuCl anchored to pre-functionalized CNTs) in the Ullmann-type coupling with aryl halides toward formation of C-N and C-O bonds. The results indicated that the stability of the catalyst was much improved and the elaborated catalytic system was efficient and recyclable. However, CNTs have not been considered as the substrate itself in the Ullmann-type reactions. But if successful, this functionalization would open new areas of CNT chemistry leading to enhanced in-solvent/matrix nanotube individualization. The copper-catalyzed Ullmann-type reaction is an attractive method for the formation of carbon-heteroatom and carbon-carbon bonds in organic synthesis. This condensation reaction is usually conducted at temperature as high as 200 oC, often in the presence of stoichiometric amounts of copper reagent and with activated aryl halides. However, a small amount of organic additive (e.g. diamines, amino acids, diols, 1,10-phenanthroline) can be applied in order to increase the solubility and stability of copper catalyst, and at the same time to allow performing the reaction under mild conditions. The copper (pre-)catalyst is prepared by in situ mixing of copper salt and the appropriate chelator. Our research is focused on the application of Ullmann-type reaction for the covalent functionalization of CNTs. Firstly, CNTs were chlorinated by using iodine trichloride (ICl3) in carbon tetrachloride (CCl4). This method involves formation of several chemical species (ICl, Cl2 and I2Cl6), but the most reactive is the dimer. The fact (that the dimer is the main individual in CCl4) is the reason for high reactivity and possibly high functionalization levels of CNTs. This method, indeed, yielded a notable amount of chlorine onto the MWCNT surface. The next step was the reaction of CNT-Cl with three substrates: aniline, iodobenzene and phenol for the formation C-N, C-C and C-O bonds, respectively, in the presence of 1,10-phenanthroline and cesium carbonate (Cs2CO3) as a base. As the CNT substrates, two multi-wall CNT (MWCNT) types were used: commercially available Nanocyl NC7000™ (9.6 nm diameter, 1.5 µm length, 90% purity) and thicker MWCNTs (in-house) synthesized in our laboratory using catalytic chemical vapour deposition (c-CVD). In-house CNTs had diameter ranging between 60-70 nm and length up to 300 µm. Since classical Ullmann reaction was found as suffering from poor yields, we have investigated the effect of various solvents (toluene, acetonitrile, dimethyl sulfoxide and N,N-dimethylformamide) on the coupling of substrates. Owing to the fact that the aryl halides show the reactivity order of I>Br>Cl>F, we have also investigated the effect of iodine presence on CNT surface on reaction yield. In this case, in first step we have used iodine monochloride instead of iodine trichloride. Finally, we have used the optimized reaction conditions with p-bromophenol and 1,2,4-trihydroxybenzene for the control of CNT dispersion.

Keywords: carbon nanotubes, coupling reaction, functionalization, Ullmann reaction

Procedia PDF Downloads 168

Authors: Pola Goldberg Oppenheimer, Stephan Hofmann, Sumeet Mahajan

Abstract:

Owing to its fingerprint molecular specificity and high sensitivity, surface-enhanced Raman scattering (SERS) is an established analytical tool for chemical and biological sensing capable of single-molecule detection. A strong Raman signal can be generated from SERS-active platforms given the analyte is within the enhanced plasmon field generated near a noble-metal nanostructured substrate. The key requirement for generating strong plasmon resonances to provide this electromagnetic enhancement is an appropriate metal surface roughness. Controlling nanoscale features for generating these regions of high electromagnetic enhancement, the so-called SERS ‘hot-spots’, is still a challenge. Significant advances have been made in SERS research, with wide-ranging techniques to generate substrates with tunable size and shape of the nanoscale roughness features. Nevertheless, the development and application of SERS has been inhibited by the irreproducibility and complexity of fabrication routes. The ability to generate straightforward, cost-effective, multiplex-able and addressable SERS substrates with high enhancements is of profound interest for miniaturised sensing devices. Carbon nanotubes (CNTs) have been concurrently, a topic of extensive research however, their applications for plasmonics has been only recently beginning to gain interest. CNTs can provide low-cost, large-active-area patternable substrates which, coupled with appropriate functionalization capable to provide advanced SERS-platforms. Herein, advanced methods to generate CNT-based SERS active detection platforms will be discussed. First, a novel electrohydrodynamic (EHD) lithographic technique will be introduced for patterning CNT-polymer composites, providing a straightforward, single-step approach for generating high-fidelity sub-micron-sized nanocomposite structures within which anisotropic CNTs are vertically aligned. The created structures are readily fine-tuned, which is an important requirement for optimizing SERS to obtain the highest enhancements with each of the EHD-CNTs individual structural units functioning as an isolated sensor. Further, gold-functionalized VACNTFs are fabricated as SERS micro-platforms. The dependence on the VACNTs’ diameters and density play an important role in the Raman signal strength, thus highlighting the importance of structural parameters, previously overlooked in designing and fabricating optimized CNTs-based SERS nanoprobes. VACNTs forests patterned into predesigned pillar structures are further utilized for multiplex detection of bio-analytes. Since CNTs exhibit electrical conductivity and unique adsorption properties, these are further harnessed in the development of novel chemical and bio-sensing platforms.

Keywords: carbon nanotubes (CNTs), EHD patterning, SERS, vertically aligned carbon nanotube forests (VACNTF)

Procedia PDF Downloads 331

Authors: Igor B. Sivaev

Abstract:

Design of molecular machines is an extraordinary growing and very important area of research that it was recognized by awarding Sauvage, Stoddart and Feringa the Nobel Prize in Chemistry in 2016 'for the design and synthesis of molecular machines'. Based on the type of motion being performed, molecular machines can be divided into two main types: molecular motors and molecular switches. Molecular switches are molecules or supramolecular complexes having bistability, i.e., the ability to exist in two or more stable forms, among which may be reversible transitions under external influence (heating, lighting, changing the medium acidity, the action of chemicals, exposure to magnetic or electric field). Molecular switches are the main structural element of any molecular electronics devices. Therefore, the design and the study of molecules and supramolecular systems capable of performing mechanical movement is an important and urgent problem of modern chemistry. There is growing interest in molecular switches and other devices of molecular electronics based on transition metal complexes; therefore choice of suitable stable organometallic unit is of great importance. An example of such unit is bis(dicarbollide) complexes of transition metals [3,3’-M(1,2-C₂B₉H₁₁)₂]ⁿ⁻. The control on the ligand rotation in such complexes can be reached by introducing substituents which could provide stabilization of certain rotamers due to specific interactions between the ligands, on the one hand, and which can participate as Lewis bases in complex formation with external metals resulting in a change in the rotation angle of the ligands, on the other hand. A series of isomeric methyl sulfide derivatives of cobalt bis(dicarbollide) complexes containing methyl sulfide substituents at boron atoms in different positions of the pentagonal face of the dicarbollide ligands [8,8’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻, rac-[4,4’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ and meso-[4,7’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ were synthesized by the reaction of CoCl₂ with the corresponding methyl sulfide carborane derivatives [10-MeS-7,8-C₂B₉H₁₁)₂]⁻ and [10-MeS-7,8-C₂B₉H₁₁)₂]⁻. In the case of asymmetrically substituted cobalt bis(dicarbollide) complexes the corresponding rac- and meso-isomers were successfully separated by column chromatography as the tetrabutylammonium salts. The compounds obtained were studied by the methods of ¹H, ¹³C, and ¹¹B NMR spectroscopy, single crystal X-ray diffraction, cyclic voltammetry, controlled potential coulometry and quantum chemical calculations. It was found that in the solid state, the transoid- and gauche-conformations of the 8,8’- and 4,4’-isomers are stabilized by four intramolecular CH···S(Me)B hydrogen bonds each one (2.683-2.712 Å and 2.709-2.752 Å, respectively), whereas gauche-conformation of the 4,7’-isomer is stabilized by two intramolecular CH···S hydrogen bonds (2.699-2.711 Å). The existence of the intramolecular CH·S(Me)B hydrogen bonding in solutions was supported by the 1H NMR spectroscopy. These data are in a good agreement with results of the quantum chemical calculations. The corresponding iron and nickel complexes were synthesized as well. The reaction of the methyl sulfide derivatives of cobalt bis(dicarbollide) with various labile transition metal complexes results in rupture of intramolecular hydrogen bonds and complexation of the methyl sulfide groups with external metal. This results in stabilization of other rotational conformation of cobalt bis(dicarbollide) and can be used in design of molecular switches. This work was supported by the Russian Science Foundation (16-13-10331).

Keywords: molecular switches, NMR spectroscopy, single crystal X-ray diffraction, transition metal bis(dicarbollide) complexes, quantum chemical calculations

Procedia PDF Downloads 172

Authors: Dimitra Das, Anuradha Mitra, Kalyan Kumar Chattopadhyay

Abstract:

Organic polymers, constructed from light elements like carbon, hydrogen, nitrogen, oxygen, sulphur, and boron atoms, are the emergent class of non-toxic, metal-free, environmental benign advanced materials. Covalent triazine-based polymers with a functional triazine group are significant class of organic materials due to their remarkable stability arising out of strong covalent bonds. They can conventionally form hydrogen bonds, favour π–π contacts, and they were recently revealed to be involved in interesting anion–π interactions. The present work mainly focuses upon the development of a single-crystalline, highly cross-linked triazine-based nitrogen-rich organic polymer with nanodendritic morphology and significant thermal stability. The polymer has been synthesized through hydrothermal treatment of melamine and ethylene glycol resulting in cross-polymerization via condensation-polymerization reaction. The crystal structure of the polymer has been evaluated by employing Rietveld whole profile fitting method. The polymer has been found to be composed of monoclinic melamine having space group P21/a. A detailed insight into the chemical structure of the as synthesized polymer has been elucidated by Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopic analysis. X-Ray Photoelectron Spectroscopic (XPS) analysis has also been carried out for further understanding of the different types of linkages required to create the backbone of the polymer. The unique rod-like morphology of the triazine based polymer has been revealed from the images obtained from Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Interestingly, this polymer has been found to selectively detect mercury (Hg²⁺) ions at an extremely low concentration through fluorescent quenching with detection limit as low as 0.03 ppb. The high toxicity of mercury ions (Hg²⁺) arise from its strong affinity towards the sulphur atoms of biological building blocks. Even a trace quantity of this metal is dangerous for human health. Furthermore, owing to its small ionic radius and high solvation energy, Hg²⁺ ions remain encapsulated by water molecules making its detection a challenging task. There are some existing reports on fluorescent-based heavy metal ion sensors using covalent organic frameworks (COFs) but reports on mercury sensing using triazine based polymers are rather undeveloped. Thus, the importance of ultra-trace detection of Hg²⁺ ions with high level of selectivity and sensitivity has contemporary significance. A plausible sensing phenomenon by the polymer has been proposed to understand the applicability of the material as a potential sensor. The impressive sensitivity of the polymer sample towards Hg²⁺ is the very first report in the field of highly crystalline triazine based polymers (without the introduction of any sulphur groups or functionalization) towards mercury ion detection through photoluminescence quenching technique. This crystalline metal-free organic polymer being cheap, non-toxic and scalable has current relevance and could be a promising candidate for Hg²⁺ ion sensing at commercial level.

Keywords: fluorescence quenching , mercury ion sensing, single-crystalline, triazine-based polymer

Procedia PDF Downloads 136

Authors: Yury S. Shpanskiy, Boris V. Kuteev

Abstract:

Development of a fusion-fission hybrid facility based on superconducting conventional tokamak DEMO-FNS runs in Russia since 2013. The main design goal is to reach the technical feasibility and outline prospects of industrial hybrid technologies providing the production of neutrons, fuel nuclides, tritium, high-temperature heat, electricity and subcritical transmutation in Fusion-Fission Hybrid Systems. The facility should operate in a steady-state mode at the fusion power of 40 MW and fission reactions of 400 MW. Major tokamak parameters are the following: major radius R=3.2 m, minor radius a=1.0 m, elongation 2.1, triangularity 0.5. The design provides the neutron wall loading of ~0.2 MW/m², the lifetime neutron fluence of ~2 MWa/m², with the surface area of the active cores and tritium breeding blanket ~100 m². Core plasma modelling showed that the neutron yield ~10¹⁹ n/s is maximal if the tritium/deuterium density ratio is 1.5-2.3. The design of the electromagnetic system (EMS) defined its basic parameters, accounting for the coils strength and stability, and identified the most problematic nodes in the toroidal field coils and the central solenoid. The EMS generates toroidal, poloidal and correcting magnetic fields necessary for the plasma shaping and confinement inside the vacuum vessel. EMC consists of eighteen superconducting toroidal field coils, eight poloidal field coils, five sections of a central solenoid, correction coils, in-vessel coils for vertical plasma control. Supporting structures, the thermal shield, and the cryostat maintain its operation. EMS operates with the pulse duration of up to 5000 hours at the plasma current up to 5 MA. The vacuum vessel (VV) is an all-welded two-layer toroidal shell placed inside the EMS. The free space between the vessel shells is filled with water and boron steel plates, which form the neutron protection of the EMS. The VV-volume is 265 m³, its mass with manifolds is 1800 tons. The nuclear blanket of DEMO-FNS facility was designed to provide functions of minor actinides transmutation, tritium production and enrichment of spent nuclear fuel. The vertical overloading of the subcritical active cores with MA was chosen as prospective. Analysis of the device neutronics and the hybrid blanket thermal-hydraulic characteristics has been performed for the system with functions covering transmutation of minor actinides, production of tritium and enrichment of spent nuclear fuel. A study of FNS facilities role in the Russian closed nuclear fuel cycle was performed. It showed that during ~100 years of operation three FNS facilities with fission power of 3 GW controlled by fusion neutron source with power of 40 MW can burn 98 tons of minor actinides and 198 tons of Pu-239 can be produced for startup loading of 20 fast reactors. Instead of Pu-239, up to 25 kg of tritium per year may be produced for startup of fusion reactors using blocks with lithium orthosilicate instead of fissile breeder blankets.

Keywords: fusion-fission hybrid system, conventional tokamak, superconducting electromagnetic system, two-layer vacuum vessel, subcritical active cores, nuclear fuel cycle

Procedia PDF Downloads 147

Authors: Sabina Żołędowska, Tadeusz Ossowski, Robert Bogdanowicz, Jacek Ryl, Paweł Rostkowski, Michał Kruczkowski, Michał Sobaszek, Zofia Cebula, Grzegorz Skowierzak, Paweł Jakóbczyk, Lilit Hovhannisyan, Paweł Ślepski, Iwona Kaczmarczyk, Mattia Pierpaoli, Bartłomiej Dec, Dawid Nidzworski

Abstract:

The circular economy of water presents a pressing environmental challenge in our society. Water contains various harmful substances, such as drugs, antibiotics, hormones, and dioxides, which can pose silent threats. Water pollution has severe consequences for aquatic ecosystems. It disrupts the balance of ecosystems by harming aquatic plants, animals, and microorganisms. Water pollution poses significant risks to human health. Exposure to toxic chemicals through contaminated water can have long-term health effects, such as cancer, developmental disorders, and hormonal imbalances. However, effective remediation systems can be implemented to remove these contaminants using electrocatalytic processes, which offer an environmentally friendly alternative to other treatment methods, and one of them is the innovative iCLARE system. The project's primary focus revolves around a few main topics: Reactor design and construction, selection of a specific type of reticulated vitreous carbon foams (RVC), analytical studies of harmful contaminants parameters and AI implementation. This high-performance electrochemical reactor will be build based on a novel type of electrode material. The proposed approach utilizes the application of reticulated vitreous carbon foams (RVC) with deposited modified metal oxides (MMO) and diamond thin films. The following setup is characterized by high surface area development and satisfactory mechanical and electrochemical properties, designed for high electrocatalytic process efficiency. The consortium validated electrode modification methods that are the base of the iCLARE product and established the procedures for the detection of chemicals detection: - deposition of metal oxides WO3 and V2O5-deposition of boron-doped diamond/nanowalls structures by CVD process. The chosen electrodes (porous Ferroterm electrodes) were stress tested for various parameters that might occur inside the iCLARE machine–corosis, the long-term structure of the electrode surface during electrochemical processes, and energetic efficacy using cyclic polarization and electrochemical impedance spectroscopy (before and after electrolysis) and dynamic electrochemical impedance spectroscopy (DEIS). This tool allows real-time monitoring of the changes at the electrode/electrolyte interphase. On the other hand, the toxicity of iCLARE chemicals and products of electrolysis are evaluated before and after the treatment using MARA examination (IBMM) and HPLC-MS-MS (NILU), giving us information about the harmfulness of using electrode material and the efficiency of iClare system in the disposal of pollutants. Implementation of data into the system that uses artificial intelligence and the possibility of practical application is in progress (SensDx).

Keywords: waste water treatement, RVC, electrocatalysis, paracetamol

Procedia PDF Downloads 88

Authors: Şeyma Dombaycıoğlu, Hilal Köse, Ali Osman Aydın, Hatem Akbulut

Abstract:

Rechargeable lithium ion batteries (LIBs) have been considered as one of the most attractive energy storage choices for laptop computers, electric vehicles and cellular phones owing to their high energy and power density. Compared with conventional carbonaceous materials, transition metal oxides (TMOs) have attracted great interests and stand out among versatile novel anode materials due to their high theoretical specific capacity, wide availability and good safety performance. ZnO, as an anode material for LIBs, has a high theoretical capacity of 978 mAh g-1, much higher than that of the conventional graphite anode (∼370 mAhg-1). However, several major problems such as poor cycleability, resulting from the severe volume expansion and contraction during the alloying-dealloying cycles with Li+ ions and the associated charge transfer process, the pulverization and the agglomeration of individual particles, which drastically reduces the total entrance/exit sites available for Li+ ions still hinder the practical use of ZnO powders as an anode material for LIBs. Therefore, a great deal of effort has been devoted to overcome these problems, and many methods have been developed. In most of these methods, it is claimed that carbon nanotubes (CNTs) will radically improve the performance of batteries, because their unique structure may especially enhance the kinetic properties of the electrodes and result in an extremely high specific charge compared with the theoretical limits of graphitic carbon. Due to outstanding properties of CNTs, MWCNT buckypaper substrate is considered a buffer material to prevent mechanical disintegration of anode material during the battery applications. As the bridge connecting the positive and negative electrodes, the electrolyte plays a critical role affecting the overall electrochemical performance of the cell including rate, capacity, durability and safety. Commercial electrolytes for Li-ion batteries normally consist of certain lithium salts and mixed organic linear and cyclic carbonate solvents. Most commonly, LiPF6 is attributed to its remarkable features including high solubility, good ionic conductivity, high dissociation constant and satisfactory electrochemical stability for commercial fabrication. Besides LiPF6, LiBF4 is well known as a conducting salt for LIBs. LiBF4 shows a better temperature stability in organic carbonate based solutions and less moisture sensitivity compared to LiPF6. In this work, free standing zinc oxide (ZnO) and multiwalled carbon nanotube (MWCNT) nanocomposite materials were prepared by a sol gel technique giving a high capacity anode material for lithium ion batteries. Electrolyte solutions (including 1 m Li+ ion) were prepared with different Li salts in glove box. For this purpose, LiPF6 and LiBF4 salts and also mixed of these salts were solved in EC:DMC solvents (1:1, w/w). CR2016 cells were assembled by using these prepared electrolyte solutions, the ZnO/MWCNT buckypaper nanocomposites as working electrodes, metallic lithium as cathode and polypropylene (PP) as separator. For investigating the effect of different Li salts on the electrochemical performance of ZnO/MWCNT nanocomposite anode material electrochemical tests were performed at room temperature.

Keywords: anode, electrolyte, Li-ion battery, ZnO/MWCNT

Procedia PDF Downloads 231

Authors: Ekta Yadav, Sukanta Bhattacharya, Brijesh Yadav, Ariel Hus, Jagjit Yadav

Abstract:

Background and Significance: Respiratory exposure to toxicants (chemicals or particulates) causes disruption of lung homeostasis leading to lung toxicity/injury manifested as pulmonary inflammation, edema, and/or other effects depending on the type and extent of exposure. This emphasizes the need for investigating toxicant type-specific mechanisms to understand therapeutic targets. Aquaporins, aka water channels, are known to play a role in lung homeostasis. Particularly, the two major lung aquaporins AQP5 and AQP1 expressed in alveolar epithelial and vasculature endothelia respectively allow for movement of the fluid between the alveolar air space and the associated vasculature. In view of this, the current study is focused on understanding the regulation of lung aquaporins and other targets during inhalation exposure to toxic chemicals (Cigarette smoke chemicals) versus toxic particles (Carbon nanoparticles) or co-exposures to understand their relevance as markers of injury and intervention. Methodologies: C57BL/6 mice (5-7 weeks old) were used in this study following an approved protocol by the University of Cincinnati Institutional Animal Care and Use Committee (IACUC). The mice were exposed via oropharyngeal aspiration to multiwall carbon nanotube (MWCNT) particles suspension once (33 ugs/mouse) followed by housing for four weeks or to Cigarette smoke Extract (CSE) using a daily dose of 30µl/mouse for four weeks, or to co-exposure using the combined regime. Control groups received vehicles following the same dosing schedule. Lung toxicity/injury was assessed in terms of homeostasis changes in the lung tissue and lumen. Exposed lungs were analyzed for transcriptional expression of specific targets (AQPs, surfactant protein A, Mucin 5b) in relation to tissue homeostasis. Total RNA from lungs extracted using TRIreagent kit was analyzed using qRT-PCR based on gene-specific primers. Total protein in bronchoalveolar lavage (BAL) fluid was determined by the DC protein estimation kit (BioRad). GraphPad Prism 5.0 (La Jolla, CA, USA) was used for all analyses. Major findings: CNT exposure alone or as co-exposure with CSE increased the total protein content in the BAL fluid (lung lumen rinse), implying compromised membrane integrity and cellular infiltration in the lung alveoli. In contrast, CSE showed no significant effect. AQP1, required for water transport across membranes of endothelial cells in lungs, was significantly upregulated in CNT exposure but downregulated in CSE exposure and showed an intermediate level of expression for the co-exposure group. Both CNT and CSE exposures had significant downregulating effects on Muc5b, and SP-A expression and the co-exposure showed either no significant effect (Muc5b) or significant downregulating effect (SP-A), suggesting an increased propensity for infection in the exposed lungs. Conclusions: The current study based on the lung toxicity mouse model showed that both toxicant types, particles (CNT) versus chemicals (CSE), cause similar downregulation of lung innate defense targets (SP-A, Muc5b) and mostly a summative effect when presented as co-exposure. However, the two toxicant types show differential induction of aquaporin-1 coinciding with the corresponding differential damage to alveolar integrity (vascular permeability). Interestingly, this implies the potential of AQP1 as a differential marker of toxicant type-specific lung injury.

Keywords: aquaporin, gene expression, lung injury, toxicant exposure

Procedia PDF Downloads 184

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

Abstract:

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

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

Procedia PDF Downloads 69