Search results for: hexagonal boron nitride
Commenced in January 2007
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Edition: International
Paper Count: 369

Search results for: hexagonal boron nitride

9 Spectroscopy and Electron Microscopy for the Characterization of CdSxSe1-x Quantum Dots in a Glass Matrix

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

Abstract:

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

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8 Synthesis and Characterisations of Cordierite Bonded Porous SiC Ceramics by Sol Infiltration Technique

Authors: Sanchita Baitalik, Nijhuma Kayal, Omprakash Chakrabarti

Abstract:

Recently SiC ceramics have been a focus of interest in the field of porous materials due to their unique combination of properties and hence they are considered as an ideal candidate for catalyst supports, thermal insulators, high-temperature structural materials, hot gas particulate separation systems etc. in different industrial processes. Several processing methods are followed for fabrication of porous SiC at low temperatures but all these methods are associated with several disadvantages. Therefore processing of porous SiC ceramics at low temperatures is still challenging. Concerning that of incorporation of secondary bond phase additives by an infiltration technique should result in a homogenous distribution of bond phase in the final ceramics. Present work is aimed to synthesis cordierite (2MgO.2Al2O3.5SiO2) bonded porous SiC ceramics following incorporation of sol-gel bond phase precursor into powder compacts of SiC and heat treating the infiltrated body at 1400 °C. In this paper the primary aim was to study the effect of infiltration of a precursor sol of cordierite into a porous SiC powder compact prepared with pore former of different particle sizes on the porosity, pore size, microstructure and the mechanical properties of the porous SiC ceramics. Cordierite sol was prepared by mixing a solution of magnesium nitrate hexahydrate and aluminium nitrate nonahydrate in 2:4 molar ratio in ethanol another solution containing tetra-ethyl orthosilicate and ethanol in 1:3 molar ratio followed by stirring for several hours. Powders of SiC (α-SiC; d50 =22.5 μm) and 10 wt. % polymer microbead of two sizes 8 and 50µm as the pore former were mixed in a suitable liquid medium, dried and pressed in the form of bars (50×20×16 mm3) at 23 MPa pressure. The well-dried bars were heat treated at 1100° C for 4 h with a hold at 750 °C for 2 h to remove the pore former. Bars were evacuated for 2 hr upto 0.3 mm Hg pressure into a vacuum chamber and infiltrated with cordierite precursor sol. The infiltrated samples were dried and the infiltration process was repeated until the weight gain became constant. Finally the infiltrated samples were sintered at 1400 °C to prepare cordierite bonded porous SiC ceramics. Porous ceramics prepared with 8 and 50 µm sized microbead exhibited lower oxidation degrees of respectively 7.8 and 4.8 % than the sample (23 %) prepared with no microbead. Depending on the size of pore former, the porosity of the final ceramic varied in the range of 36 to 40 vol. % with a variation of flexural strength from 33.7 to 24.6 MPa. XRD analysis showed major crystalline phases of the ceramics as SiC, SiO2 and cordierite. Two forms of cordierite, α-(hexagonal) and µ-(cubic), were detected by the XRD analysis. The SiC particles were observed to be bonded both by cristobalite with fish scale morphology and cordierite with rod shape morphology and thereby formed a porous network. The material and mechanical properties of cordierite bonded porous SiC ceramics are good in agreement to carry out further studies like thermal shock, corrosion resistance etc.

Keywords: cordierite, infiltration technique, porous ceramics, sol-gel

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7 Elaboration and Characterization of in-situ CrC- Ni(Al, Cr) Composites Elaborated from Ni and Cr₂AlC Precursors

Authors: A. Chiker, A. Benamor, A. Haddad, Y. Hadji, M. Hadji

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Metal matrix composites (MMCs) have been of big interest for a few decades. Their major drawback lies in their enhanced mechanical performance over unreinforced alloys. They found ground in many engineering fields, such as aeronautics, aerospace, automotive, and other structural applications. One of the most used alloys as a matrix is nickel alloys, which meet the need for high-temperature mechanical properties; some attempts have been made to develop nickel base composites reinforced by high melt point and high modulus particulates. Among the carbides used as reinforcing particulates, chromium carbide is interesting for wear applications; it is widely used as a tribological coating material in high-temperature applications requiring high wear resistance and hardness. Moreover, a set of properties make it suitable for use in MMCs, such as toughness, the good corrosion and oxidation resistance of its three polymorphs -the cubic (Cr23C6), the hexagonal (Cr7C3), and the orthorhombic (Cr3C2)-, and it’s coefficient of thermal expansion that is almost equal to that of metals. The in-situ synthesis of CrC-reinforced Ni matrix composites could be achieved by the powder metallurgy route. To ensure the in-situ reactions during the sintering process, the use of phase precursors is necessary. Recently, new precursor materials have been proposed; these materials are called MAX phases. The MAX phases are thermodynamically stable nano-laminated materials displaying unusual and sometimes unique properties. These novel phases possess Mn+1AXn chemistry, where n is 1, 2, or 3, M is an early transition metal element, A is an A-group element, and X is C or N. Herein, the pressureless sintering method is used to elaborate Ni/Cr2AlC composites. Four composites were elaborated from 5, 10, 15 and 20 wt% of Cr2AlC MAX phase precursor which fully reacted with Ni-matrix at 1100 °C sintering temperature for 4 h in argon atmosphere. XRD results showed that Cr2AlC MAX phase was totally decomposed forming chromium carbide Cr7C3, and the released Al and Cr atoms diffused in Ni matrix giving rise to γ-Ni(Al,Cr) solid solution and γ’-Ni3(Al,Cr) intermetallic. Scanning Electron Microscopy (SEM) of the elaborated samples showed the presence of nanosized Cr7C3 reinforcing particles embedded in the Ni metal matrix, which have a direct impact on the tribological properties of the composites and their hardness. All the composites exhibited higher hardness than pure Ni; whereas adding 15 wt% of Cr2AlC gives the highest hardness (1.85 GPa). Using a ball-on-disc tribometer, dry sliding tests for the elaborated composites against 100Cr6 steel ball were studied under different applied loads. The microstructures and worn surface characteristics were then analyzed using SEM and Raman spectroscopy. The results show that all the composites exhibited better wear resistance compared to pure Ni, which could be explained by the formation of a lubricious tribo-layer during sliding and the good bonding between the Ni matrix and the reinforcing phases.

Keywords: composites, microscopy, sintering, wear

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6 Oxidative Dehydrogenation and Hydrogenation of Malic Acid over Transition Metal Oxides

Authors: Gheorghiţa Mitran, Adriana Urdă, Mihaela Florea, Octavian Dumitru Pavel, Florentina Neaţu

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Oxidative dehydrogenation and hydrogenation reactions of L-malic acid are interesting ways for its transformation into valuable products, including oxaloacetic, pyruvic and malonic acids but also 1,4-butanediol and 1,2,4-butanetriol. Keto acids have a range of applicationsin many chemical syntheses as pharmaceuticals, food additives and cosmetics. 3-Hydroxybutyrolactone and 1,2,4-butanetriol are used for the synthesis of chiral pharmaceuticals and other fine chemicals, while 1,4-butanediol can be used for organic syntheses, such as polybutylene succinate (PBS), polybutylene terephthalate (PBT), and for production of tetrahydrofuran (THF). L-malic acid is a non-toxic and natural organic acid present in fruits, and it is the main component of wine alongside tartaric acid representing about 90% of the wine total acidity. Iron oxides dopped with cobalt (CoxFe3-xO4; x= 0; 0.05; 0.1; 0.15) were studied as catalysts in these reactions. There is no mention in the literature of non-noble transition metal catalysts for these reactions. The method used for catalysts preparation was coprecipitation, whileBET XRD, XPS, FTIR and UV-VIS spectroscopy were used for the physicochemical properties evaluation.TheXRD patterns revealed the presence of α-Fe2O3 rhombohedral hematite structure, with cobalt atoms well dispersed and embedded in this structure. The studied samples are highly crystalline, with a crystallite size ranged from 58 to 65 nm. The optical absorption properties were investigated using UV-Vis spectroscopy, emphasizing the presence of bands that correspond with the reported hematite nanoparticle. Likewise, the presence of bands corresponding to lattice vibration of hexagonal hematite structurehas been evidenced in DRIFT spectra. Oxidative dehydrogenation of malic acid was studied using as solvents for malic acid ethanol or water(2, 5 and 10% malic acid in 5 mL solvent)at room temperature, while the hydrogenation reaction was evaluated in water as solvent (5%), in the presence of 1% catalyst. The oxidation of malic acid into oxaloacetic acid is the first step, after that, oxaloacetic acid is rapidly decarboxylated to malonic acid or pyruvic acid, depending on the active site. The concentration of malic acid in solution, it, in turn, has an influence on conversionthis decreases when the concentration of malic acid in the solution is high. The spent catalysts after the oxidative dehydrogenation of malic acid in ethanol were characterized by DRIFT spectroscopy and the presence of oxaloacetic, pyruvic and malonicacids, along with unreacted malic acidwere observed on the surface. The increase of the ratio of Co/Fe on the surface has an influence on the malic acid conversion and on the pyruvic acid yield, while the yield of malonic acid is influenced by the percentage of iron on the surface (determined from XPS). Oxaloacetic acid yield reaches a maximumat one hour of reaction, being higher when ethanol is used as a solvent, after which it suddenly decreases. The hydrogenation of malic acid occurs by consecutive reactions with the production of 3-hydroxy-butyrolactone, 1,2,4-butanetriol and 1,4-butanediol. Malic acid conversion increases with cobalt loading increasing up to Co/Fe ratio of 0.1, after which it has a slight decrease, while the yield in 1,4-butanediol is directly proportional to the cobalt content.

Keywords: malic acid, oxidative dehydrogenation, hydrogenation, oxaloacetic acid

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5 Transition Metal Bis(Dicarbollide) Complexes in Design of Molecular Switches

Authors: Igor B. Sivaev

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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

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4 Thermally Stable Crystalline Triazine-Based Organic Polymeric Nanodendrites for Mercury(2+) Ion Sensing

Authors: Dimitra Das, Anuradha Mitra, Kalyan Kumar Chattopadhyay

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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

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3 Development of DEMO-FNS Hybrid Facility and Its Integration in Russian Nuclear Fuel Cycle

Authors: Yury S. Shpanskiy, Boris V. Kuteev

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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

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2 Made on Land, Ends Up in the Water "I-Clare" Intelligent Remediation System for Removal of Harmful Contaminants in Water using Modified Reticulated Vitreous Carbon Foam

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

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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

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1 Development of Anti-Fouling Surface Features Bioinspired by the Patterned Micro-Textures of the Scophthalmus rhombus (Brill)

Authors: Ivan Maguire, Alan Barrett, Alex Forte, Sandra Kwiatkowska, Rohit Mishra, Jens Ducrèe, Fiona Regan

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Biofouling is defined as the gradual accumulation of Biomimetics refers to the use and imitation of principles copied from nature. Biomimetics has found interest across many commercial disciplines. Among many biological objects and their functions, aquatic animals deserve a special attention due to their antimicrobial capabilities resulting from chemical composition, surface topography or other behavioural defences, which can be used as an inspiration for antifouling technology. Marine biofouling has detrimental effects on seagoing vessels, both commercial and leisure, as well as on oceanographic sensors, offshore drilling rigs, and aquaculture installations. Sensor optics, membranes, housings and platforms can become fouled leading to problems with sensor performance and data integrity. While many anti-fouling solutions are currently being investigated as a cost-cutting measure, biofouling settlement may also be prevented by creating a surface that does not satisfy the settlement conditions. Brill (Scophthalmus rhombus) is a small flatfish occurring in marine waters of Mediterranean as well as Norway and Iceland. It inhabits sandy and muddy coastal waters from 5 to 80 meters. Its skin colour changes depending on environment, but generally is brownish with light and dark freckles, with creamy underside. Brill is oval in shape and its flesh is white. The aim of this study is to translate the unique micro-topography of the brill scale, to design marine inspired biomimetic surface coating and test it against a typical fouling organism. Following extensive study of scale topography of the brill fish (Scophthalmus rhombus) and the settlement behaviour of the diatom species Psammodictyon sp. via SEM, two state-of-the-art antifouling surface solutions were designed and investigated; A brill fish scale bioinspired surface pattern platform (BFD), and generic and uniformly-arrayed, circular micropillar platform (MPD), with offsets based on diatom species settlement behaviour. The BFD approach consists of different ~5 μm by ~90 μm Brill-replica patterns, grown to a 5 μm height, in a linear array pattern. The MPD approach utilises hexagonal-packed cylindrical pillars 10.6 μm in diameter, grown to a height of 5 μm, with vertical offset of 15 μm and horizontal offset of 26.6 μm. Photolithography was employed for microstructure growth, with a polydimethylsiloxane (PDMS) chip-based used as a testbed for diatom adhesion on both platforms. Settlement and adhesion tests were performed using this PDMS microfluidic chip through subjugation to centrifugal force via an in-house developed ‘spin-stand’ which features a motor, in combination with a high-resolution camera, for real-time observing diatom release from PDMS material. Diatom adhesion strength can therefore be determined based on the centrifugal force generated at varying rotational speeds. It is hoped that both the replica and bio-inspired solutions will give comparable anti-fouling results to these synthetic surfaces, whilst also assisting in determining whether anti-fouling solutions should predominantly be investigating either fully bioreplica-based, or a bioinspired, synthetically-based design.

Keywords: anti-fouling applications, bio-inspired microstructures, centrifugal microfluidics, surface modification

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