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36 Biomimetic Dinitrosyl Iron Complexes: A Synthetic, Structural, and Spectroscopic Study
Authors: Lijuan Li
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Nitric oxide (NO) has become a fascinating entity in biological chemistry over the past few years. It is a gaseous lipophilic radical molecule that plays important roles in several physiological and pathophysiological processes in mammals, including activating the immune response, serving as a neurotransmitter, regulating the cardiovascular system, and acting as an endothelium-derived relaxing factor. NO functions in eukaryotes both as a signal molecule at nanomolar concentrations and as a cytotoxic agent at micromolar concentrations. The latter arises from the ability of NO to react readily with a variety of cellular targets leading to thiol S-nitrosation, amino acid N-nitrosation, and nitrosative DNA damage. Nitric oxide can readily bind to metals to give metal-nitrosyl (M-NO) complexes. Some of these species are known to play roles in biological NO storage and transport. These complexes have different biological, photochemical, or spectroscopic properties due to distinctive structural features. These recent discoveries have spawned a great interest in the development of transition metal complexes containing NO, particularly its iron complexes that are central to the role of nitric oxide in the body. Spectroscopic evidence would appear to implicate species of “Fe(NO)2+” type in a variety of processes ranging from polymerization, carcinogenesis, to nitric oxide stores. Our research focuses on isolation and structural studies of non-heme iron nitrosyls that mimic biologically active compounds and can potentially be used for anticancer drug therapy. We have shown that reactions between Fe(NO)2(CO)2 and a series of imidazoles generated new non-heme iron nitrosyls of the form Fe(NO)2(L)2 [L = imidazole, 1-methylimidazole, 4-methylimidazole, benzimidazole, 5,6-dimethylbenzimidazole, and L-histidine] and a tetrameric cluster of [Fe(NO)2(L)]4 (L=Im, 4-MeIm, BzIm, and Me2BzIm), resulted from the interactions of Fe(NO)2 with a series of substituted imidazoles was prepared. Recently, a series of sulfur bridged iron di nitrosyl complexes with the general formula of [Fe(µ-RS)(NO)2]2 (R = n-Pr, t-Bu, 6-methyl-2-pyridyl, and 4,6-dimethyl-2-pyrimidyl), were synthesized by the reaction of Fe(NO)2(CO)2 with thiols or thiolates. Their structures and properties were studied by IR, UV-vis, 1H-NMR, EPR, electrochemistry, X-ray diffraction analysis and DFT calculations. IR spectra of these complexes display one weak and two strong NO stretching frequencies (νNO) in solution, but only two strong νNO in solid. DFT calculations suggest that two spatial isomers of these complexes bear 3 Kcal energy difference in solution. The paramagnetic complexes [Fe2(µ-RS)2(NO)4]-, have also been investigated by EPR spectroscopy. Interestingly, the EPR spectra of complexes exhibit an isotropic signal of g = 1.998 - 2.004 without hyperfine splitting. The observations are consistent with the results of calculations, which reveal that the unpaired electron dominantly delocalize over the two sulfur and two iron atoms. The difference of the g values between the reduced form of iron-sulfur clusters and the typical monomeric di nitrosyl iron complexes is explained, for the first time, by of the difference in unpaired electron distributions between the two types of complexes, which provides the theoretical basis for the use of g value as a spectroscopic tool to differentiate these biologically active complexes.Keywords: di nitrosyl iron complex, metal nitrosyl, non-heme iron, nitric oxide
Procedia PDF Downloads 30335 The Effects of Lithofacies on Oil Enrichment in Lucaogou Formation Fine-Grained Sedimentary Rocks in Santanghu Basin, China
Authors: Guoheng Liu, Zhilong Huang
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For more than the past ten years, oil and gas production from marine shale such as the Barnett shale. In addition, in recent years, major breakthroughs have also been made in lacustrine shale gas exploration, such as the Yanchang Formation of the Ordos Basin in China. Lucaogou Formation shale, which is also lacustrine shale, has also yielded a high production in recent years, for wells such as M1, M6, and ML2, yielding a daily oil production of 5.6 tons, 37.4 tons and 13.56 tons, respectively. Lithologic identification and classification of reservoirs are the base and keys to oil and gas exploration. Lithology and lithofacies obviously control the distribution of oil and gas in lithological reservoirs, so it is of great significance to describe characteristics of lithology and lithofacies of reservoirs finely. Lithofacies is an intrinsic property of rock formed under certain conditions of sedimentation. Fine-grained sedimentary rocks such as shale formed under different sedimentary conditions display great particularity and distinctiveness. Hence, to our best knowledge, no constant and unified criteria and methods exist for fine-grained sedimentary rocks regarding lithofacies definition and classification. Consequently, multi-parameters and multi-disciplines are necessary. A series of qualitative descriptions and quantitative analysis were used to figure out the lithofacies characteristics and its effect on oil accumulation of Lucaogou formation fine-grained sedimentary rocks in Santanghu basin. The qualitative description includes core description, petrographic thin section observation, fluorescent thin-section observation, cathode luminescence observation and scanning electron microscope observation. The quantitative analyses include X-ray diffraction, total organic content analysis, ROCK-EVAL.II Methodology, soxhlet extraction, porosity and permeability analysis and oil saturation analysis. Three types of lithofacies were mainly well-developed in this study area, which is organic-rich massive shale lithofacies, organic-rich laminated and cloddy hybrid sedimentary lithofacies and organic-lean massive carbonate lithofacies. Organic-rich massive shale lithofacies mainly include massive shale and tuffaceous shale, of which quartz and clay minerals are the major components. Organic-rich laminated and cloddy hybrid sedimentary lithofacies contain lamina and cloddy structure. Rocks from this lithofacies chiefly consist of dolomite and quartz. Organic-lean massive carbonate lithofacies mainly contains massive bedding fine-grained carbonate rocks, of which fine-grained dolomite accounts for the main part. Organic-rich massive shale lithofacies contain the highest content of free hydrocarbon and solid organic matter. Moreover, more pores were developed in organic-rich massive shale lithofacies. Organic-lean massive carbonate lithofacies contain the lowest content solid organic matter and develop the least amount of pores. Organic-rich laminated and cloddy hybrid sedimentary lithofacies develop the largest number of cracks and fractures. To sum up, organic-rich massive shale lithofacies is the most favorable type of lithofacies. Organic-lean massive carbonate lithofacies is impossible for large scale oil accumulation.Keywords: lithofacies classification, tuffaceous shale, oil enrichment, Lucaogou formation
Procedia PDF Downloads 21834 The Effect of Ionic Liquid Anion Type on the Properties of TiO2 Particles
Authors: Marta Paszkiewicz, Justyna Łuczak, Martyna Marchelek, Adriana Zaleska-Medynska
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In recent years, photocatalytical processes have been intensively investigated for destruction of pollutants, hydrogen evolution, disinfection of water, air and surfaces, for the construction of self-cleaning materials (tiles, glass, fibres, etc.). Titanium dioxide (TiO2) is the most popular material used in heterogeneous photocatalysis due to its excellent properties, such as high stability, chemical inertness, non-toxicity and low cost. It is well known that morphology and microstructure of TiO2 significantly influence the photocatalytic activity. This characteristics as well as other physical and structural properties of photocatalysts, i.e., specific surface area or density of crystalline defects, could be controlled by preparation route. In this regard, TiO2 particles can be obtained by sol-gel, hydrothermal, sonochemical methods, chemical vapour deposition and alternatively, by ionothermal synthesis using ionic liquids (ILs). In the TiO2 particles synthesis ILs may play a role of a solvent, soft template, reagent, agent promoting reduction of the precursor or particles stabilizer during synthesis of inorganic materials. In this work, the effect of the ILs anion type on morphology and photoactivity of TiO2 is presented. The preparation of TiO2 microparticles with spherical structure was successfully achieved by solvothermal method, using tetra-tert-butyl orthotitatane (TBOT) as the precursor. The reaction process was assisted by an ionic liquids 1-butyl-3-methylimidazolium bromide [BMIM][Br], 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] and 1-butyl-3-methylimidazolium haxafluorophosphate [BMIM][PF6]. Various molar ratios of all ILs to TBOT (IL:TBOT) were chosen. For comparison, reference TiO2 was prepared using the same method without IL addition. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brenauer-Emmett-Teller surface area (BET), NCHS analysis, and FTIR spectroscopy were used to characterize the surface properties of the samples. The photocatalytic activity was investigated by means of phenol photodegradation in the aqueous phase as a model pollutant, as well as formation of hydroxyl radicals based on detection of fluorescent product of coumarine hydroxylation. The analysis results showed that the TiO2 microspheres had spherical structure with the diameters ranging from 1 to 6 µm. The TEM micrographs gave a bright observation of the samples in which the particles were comprised of inter-aggregated crystals. It could be also observed that the IL-assisted TiO2 microspheres are not hollow, which provides additional information about possible formation mechanism. Application of the ILs results in rise of the photocatalytic activity as well as BET surface area of TiO2 as compared to pure TiO2. The results of the formation of 7-hydroxycoumarin indicated that the increased amount of ·OH produced at the surface of excited TiO2 for samples TiO2_ILs well correlated with more efficient degradation of phenol. NCHS analysis showed that ionic liquids remained on the TiO2 surface confirming structure directing role of that compounds.Keywords: heterogeneous photocatalysis, IL-assisted synthesis, ionic liquids, TiO2
Procedia PDF Downloads 26633 Nanoparticle Supported, Magnetically Separable Metalloporphyrin as an Efficient Retrievable Heterogeneous Nanocatalyst in Oxidation Reactions
Authors: Anahita Mortazavi Manesh, Mojtaba Bagherzadeh
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Metalloporphyrins are well known to mimic the activity of monooxygenase enzymes. In this regard, metalloporphyrin complexes have been largely employed as valuable biomimetic catalysts, owing to the critical roles they play in oxygen transfer processes in catalytic oxidation reactions. Investigating in this area is based on different strategies to design selective, stable and high turnover catalytic systems. Immobilization of expensive metalloporphyrin catalysts onto supports appears to be a good way to improve their stability, selectivity and the catalytic performance because of the support environment and other advantages with respect to recovery, reuse. In other words, supporting metalloporphyrins provides a physical separation of active sites, thus minimizing catalyst self-destruction and dimerization of unhindered metalloporphyrins. Furthermore, heterogeneous catalytic oxidations have become an important target since their process are used in industry, helping to minimize the problems of industrial waste treatment. Hence, the immobilization of these biomimetic catalysts is much desired. An attractive approach is the preparation of the heterogeneous catalyst involves immobilization of complexes on silica coated magnetic nano-particles. Fe3O4@SiO2 magnetic nanoparticles have been studied extensively due to their superparamagnetism property, large surface area to volume ratio and easy functionalization. Using heterogenized homogeneous catalysts is an attractive option to facile separation of catalyst, simplified product work-up and continuity of catalytic system. Homogeneous catalysts immobilized on magnetic nanoparticles (MNPs) surface occupy a unique position due to combining the advantages of both homogeneous and heterogeneous catalysts. In addition, superparamagnetic nature of MNPs enable very simple separation of the immobilized catalysts from the reaction mixture using an external magnet. In the present work, an efficient heterogeneous catalyst was prepared by immobilizing manganese porphyrin on functionalized magnetic nanoparticles through the amino propyl linkage. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, atomic absorption spectroscopy, UV-Vis spectroscopy, and scanning electron microscopy. Application of immobilized metalloporphyrin in the oxidation of various organic substrates was explored using Gas chromatographic (GC) analyses. The results showed that the supported Mn-porphyrin catalyst (Fe3O4@SiO2-NH2@MnPor) is an efficient and reusable catalyst in oxidation reactions. Our catalytic system exhibits high catalytic activity in terms of turnover number (TON) and reaction conditions. Leaching and recycling experiments revealed that nanocatalyst can be recovered several times without loss of activity and magnetic properties. The most important advantage of this heterogenized catalytic system is the simplicity of the catalyst separation in which the catalyst can be separated from the reaction mixture by applying a magnet. Furthermore, the separation and reuse of the magnetic Fe3O4 nanoparticles were very effective and economical.Keywords: Fe3O4 nanoparticle, immobilized metalloporphyrin, magnetically separable nanocatalyst, oxidation reactions
Procedia PDF Downloads 29632 Immobilization of Superoxide Dismutase Enzyme on Layered Double Hydroxide Nanoparticles
Authors: Istvan Szilagyi, Marko Pavlovic, Paul Rouster
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Antioxidant enzymes are the most efficient defense systems against reactive oxygen species, which cause severe damage in living organisms and industrial products. However, their supplementation is problematic due to their high sensitivity to the environmental conditions. Immobilization on carrier nanoparticles is a promising research direction towards the improvement of their functional and colloidal stability. In that way, their applications in biomedical treatments and manufacturing processes in the food, textile and cosmetic industry can be extended. The main goal of the present research was to prepare and formulate antioxidant bionanocomposites composed of superoxide dismutase (SOD) enzyme, anionic clay (layered double hydroxide, LDH) nanoparticle and heparin (HEP) polyelectrolyte. To characterize the structure and the colloidal stability of the obtained compounds in suspension and solid state, electrophoresis, dynamic light scattering, transmission electron microscopy, spectrophotometry, thermogravimetry, X-ray diffraction, infrared and fluorescence spectroscopy were used as experimental techniques. LDH-SOD composite was synthesized by enzyme immobilization on the clay particles via electrostatic and hydrophobic interactions, which resulted in a strong adsorption of the SOD on the LDH surface, i.e., no enzyme leakage was observed once the material was suspended in aqueous solutions. However, the LDH-SOD showed only limited resistance against salt-induced aggregation and large irregularly shaped clusters formed during short term interval even at lower ionic strengths. Since sufficiently high colloidal stability is a key requirement in most of the applications mentioned above, the nanocomposite was coated with HEP polyelectrolyte to develop highly stable suspensions of primary LDH-SOD-HEP particles. HEP is a natural anticoagulant with one of the highest negative line charge density among the known macromolecules. The experimental results indicated that it strongly adsorbed on the oppositely charged LDH-SOD surface leading to charge inversion and to the formation of negatively charged LDH-SOD-HEP. The obtained hybrid materials formed stable suspension even under extreme conditions, where classical colloid chemistry theories predict rapid aggregation of the particles and unstable suspensions. Such a stabilization effect originated from electrostatic repulsion between the particles of the same sign of charge as well as from steric repulsion due to the osmotic pressure raised during the overlap of the polyelectrolyte chains adsorbed on the surface. In addition, the SOD enzyme kept its structural and functional integrity during the immobilization and coating processes and hence, the LDH-SOD-HEP bionanocomposite possessed excellent activity in decomposition of superoxide radical anions, as revealed in biochemical test reactions. In conclusion, due to the improved colloidal stability and the good efficiency in scavenging superoxide radical ions, the developed enzymatic system is a promising antioxidant candidate for biomedical or other manufacturing processes, wherever the aim is to decompose reactive oxygen species in suspensions.Keywords: clay, enzyme, polyelectrolyte, formulation
Procedia PDF Downloads 26631 Collagen/Hydroxyapatite Compositions Doped with Transitional Metals for Bone Tissue Engineering Applications
Authors: D. Ficai, A. Ficai, D. Gudovan, I. A. Gudovan, I. Ardelean, R. Trusca, E. Andronescu, V. Mitran, A. Cimpean
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In the last years, scientists struggled hardly to mimic bone structures to develop implants and biostructures which present higher biocompatibility and reduced rejection rate. One way to obtain this goal is to use similar materials as that of bone, namely collagen/hydroxyapatite composite materials. However, it is very important to tailor both compositions but also the microstructure of the bone that would ensure both the optimal osteointegartion and the mechanical properties required by the application. In this study, new collagen/hydroxyapatites composite materials doped with Cu, Li, Mn, Zn were successfully prepared. The synthesis method is described below: weight the Ca(OH)₂ mass, i.e., 7,3067g, and ZnCl₂ (0.134g), CuSO₄ (0.159g), LiCO₃ (0.133g), MnCl₂.4H₂O (0.1971g), and suspend in 100ml distilled water under magnetic stirring. The solution thus obtained is added a solution of NaH₂PO₄*H2O (8.247g dissolved in 50ml distilled water) under slow dropping of 1 ml/min followed by adjusting the pH to 9.5 with HCl and finally filter and wash until neutral pH. The as-obtained slurry was dried in the oven at 80°C and then calcined at 600°C in order to ensure a proper purification of the final product of organic phases, also inducing a proper sterilization of the mixture before insertion into the collagen matrix. The collagen/hydroxyapatite composite materials are tailored from morphological point of view to optimize their biocompatibility and bio-integration against mechanical properties whereas the addition of the dopants is aimed to improve the biological activity of the samples. The addition of transitional metals can improve the biocompatibility and especially the osteoblasts adhesion (Mn²⁺) or to induce slightly better osteoblast differentiation of the osteoblast, Zn²⁺ being a cofactor for many enzymes including those responsible for cell differentiation. If the amount is too high, the final material can become toxic and lose all of its biocompatibility. In order to achieve a good biocompatibility and not reach the cytotoxic effect, the amount of transitional metals added has to be maintained at low levels (0.5% molar). The amount of transitional metals entering into the elemental cell of HA will be verified using inductively-coupled plasma mass spectrometric system. This highly sensitive technique is necessary, because, at such low levels of transitional metals, the difference between biocompatible and cytotoxic is a very thin line, thus requiring proper and thorough investigation using a precise technique. In order to determine the structure and morphology of the obtained composite materials, IR spectroscopy, X-Ray diffraction (XRD), scanning electron microscopy (SEM), and Energy Dispersive X-Ray Spectrometry (EDS) were used. Acknowledgment: The present work was possible due to the EU-funding grant POSCCE-A2O2.2.1-2013-1, Project No. 638/12.03.2014, code SMIS-CSNR 48652. The financial contribution received from the national project “Biomimetic porous structures obtained by 3D printing developed for bone tissue engineering (BIOGRAFTPRINT), No. 127PED/2017 is also highly acknowledged.Keywords: collagen, composite materials, hydroxyapatite, bone tissue engineering
Procedia PDF Downloads 20530 Evaluation of Biological and Confinement Properties of a Bone Substitute to in Situ Preparation Based on Demineralized Bone Matrix for Bone Tissue Regeneration
Authors: Aura Maria Lopera Echavarria, Angela Maria Lema Perez, Daniela Medrano David, Pedronel Araque Marin, Marta Elena Londoño Lopez
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Bone regeneration is the process by which the formation of new bone is stimulated. Bone fractures can originate at any time due to trauma, infections, tumors, congenital malformations or skeletal diseases. Currently there are different strategies to treat bone defects that in some cases, regeneration does not occur on its own. That is why they are treated with bone substitutes, which provide a necessary environment for the cells to synthesize new bone. The Demineralized Bone Matrix (DBM) is widely used as a bone implant due to its good properties, such as osteoinduction and bioactivity. However, the use of DBM is limited, because its presentation is powder, which is difficult to implant with precision and is susceptible to migrating to other sites through blood flow. That is why the DBM is commonly incorporated into a variety of vehicles or carriers. The objective of this project is to evaluate the bioactive and confinement properties of a bone substitute based on demineralized bone matrix (DBM). Also, structural and morphological properties were evaluated. Bone substitute was obtained from EIA Biomaterials Laboratory of EIA University and the DBM was facilitated by Tissue Bank Foundation. Morphological and structural properties were evaluated by scanning electron microscopy (SEM), X-ray diffraction (DRX) and Fourier transform infrared spectroscopy with total attenuated reflection (FTIR-ATR). Water absorption capacity and degradation were also evaluated during three months. The cytotoxicity was evaluated by the MTT test. The bioactivity of the bone substitute was evaluated through immersion of the samples in simulated body fluid during four weeks. Confinement tests were performed on tibial fragments of a human donor with bone defects of determined size, to ensure that the substitute remains in the defect despite the continuous flow of fluid. According of the knowledge of the authors, the methodology for evaluating samples in a confined environment has not been evaluated before in real human bones. The morphology of the samples showed irregular surface and presented some porosity. DRX confirmed a semi-crystalline structure. The FTIR-ATR determined the organic and inorganic phase of the sample. The degradation and absorption measurements stablished a loss of 3% and 150% in one month respectively. The MTT showed that the system is not cytotoxic. Apatite clusters formed from the first week were visualized by SEM and confirmed by EDS. These calcium phosphates are necessary to stimulate bone regeneration and thanks to the porosity of the developed material, osteinduction and osteoconduction are possible. The results of the in vitro evaluation of the confinement of the material showed that the migration of the bone filling to other sites is negligible, although the samples were subjected to the passage of simulated body fluid. The bone substitute, putty type, showed stability, is bioactive, non-cytotoxic and has handling properties for specialists at the time of implantation. The obtained system allows to maintain the osteoinductive properties of DBM and it can fill completely fractures in any way; however, it does not provide a structural support, that is, it should only be used to treat fractures without requiring a mechanical load.Keywords: bone regeneration, cytotoxicity, demineralized bone matrix, hydrogel
Procedia PDF Downloads 11929 Piezotronic Effect on Electrical Characteristics of Zinc Oxide Varistors
Authors: Nadine Raidl, Benjamin Kaufmann, Michael Hofstätter, Peter Supancic
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If polycrystalline ZnO is properly doped and sintered under very specific conditions, it shows unique electrical properties, which are indispensable for today’s electronic industries, where it is used as the number one overvoltage protection material. Under a critical voltage, the polycrystalline bulk exhibits high electrical resistance but becomes suddenly up to twelve magnitudes more conductive if this voltage limit is exceeded (i.e., varistor effect). It is known that these peerless properties have their origin in the grain boundaries of the material. Electric charge is accumulated in the boundaries, causing a depletion layer in their vicinity and forming potential barriers (so-called Double Schottky Barriers, or DSB) which are responsible for the highly non-linear conductivity. Since ZnO is a piezoelectric material, mechanical stresses induce polarisation charges that modify the DSB heights and as a result the global electrical characteristics (i.e., piezotronic effect). In this work, a finite element method was used to simulate emerging stresses on individual grains in the bulk. Besides, experimental efforts were made to testify a coherent model that could explain this influence. Electron back scattering diffraction was used to identify grain orientations. With the help of wet chemical etching, grain polarization was determined. Micro lock-in infrared thermography (MLIRT) was applied to detect current paths through the material, and a micro 4-point probes method system (M4PPS) was employed to investigate current-voltage characteristics between single grains. Bulk samples were tested under uniaxial pressure. It was found that the conductivity can increase by up to three orders of magnitude with increasing stress. Through in-situ MLIRT, it could be shown that this effect is caused by the activation of additional current paths in the material. Further, compressive tests were performed on miniaturized samples with grain paths containing solely one or two grain boundaries. The tests evinced both an increase of the conductivity, as observed for the bulk, as well as a decreased conductivity. This phenomenon has been predicted theoretically and can be explained by piezotronically induced surface charges that have an impact on the DSB at the grain boundaries. Depending on grain orientation and stress direction, DSB can be raised or lowered. Also, the experiments revealed that the conductivity within one single specimen can increase and decrease, depending on the current direction. This novel finding indicates the existence of asymmetric Double Schottky Barriers, which was furthermore proved by complementary methods. MLIRT studies showed that the intensity of heat generation within individual current paths is dependent on the direction of the stimulating current. M4PPS was used to study the relationship between the I-V characteristics of single grain boundaries and grain orientation and revealed asymmetric behavior for very specific orientation configurations. A new model for the Double Schottky Barrier, taking into account the natural asymmetry and explaining the experimental results, will be given.Keywords: Asymmetric Double Schottky Barrier, piezotronic, varistor, zinc oxide
Procedia PDF Downloads 26628 Ordered Mesoporous Carbons of Different Morphology for Loading and Controlled Release of Active Pharmaceutical Ingredients
Authors: Aleksander Ejsmont, Aleksandra Galarda, Joanna Goscianska
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Smart porous carriers with defined structure and physicochemical properties are required for releasing the therapeutic drug with precise control of delivery time and location in the body. Due to their non-toxicity, ordered structure, chemical, and thermal stability, mesoporous carbons can be considered as modern carriers for active pharmaceutical ingredients (APIs) whose effectiveness needs frequent dosing algorithms. Such an API-carrier system, if programmed precisely, may stabilize the pharmaceutical and increase its dissolution leading to enhanced bioavailability. The substance conjugated with the material, through its prior adsorption, can later be successfully applied internally to the organism, as well as externally if the API release is feasible under these conditions. In the present study, ordered mesoporous carbons of different morphologies and structures, prepared by hard template method, were applied as carriers in the adsorption and controlled release of active pharmaceutical ingredients. In the first stage, the carbon materials were synthesized and functionalized with carboxylic groups by chemical oxidation using ammonium persulfate solution and then with amine groups. Materials obtained were thoroughly characterized with respect to morphology (scanning electron microscopy), structure (X-ray diffraction, transmission electron microscopy), characteristic functional groups (FT-IR spectroscopy), acid-base nature of surface groups (Boehm titration), parameters of the porous structure (low-temperature nitrogen adsorption) and thermal stability (TG analysis). This was followed by a series of tests of adsorption and release of paracetamol, benzocaine, and losartan potassium. Drug release experiments were performed in the simulated gastric fluid of pH 1.2 and phosphate buffer of pH 7.2 or 6.8 at 37.0 °C. The XRD patterns in the small-angle range and TEM images revealed that functionalization of mesoporous carbons with carboxylic or amine groups leads to the decreased ordering of their structure. Moreover, the modification caused a considerable reduction of the carbon-specific surface area and pore volume, but it simultaneously resulted in changing their acid-base properties. Mesoporous carbon materials exhibit different morphologies, which affect the host-guest interactions during the adsorption process of active pharmaceutical ingredients. All mesoporous carbons show high adsorption capacity towards drugs. The sorption capacity of materials is mainly affected by BET surface area and the structure/size matching between adsorbent and adsorbate. Selected APIs are linked to the surface of carbon materials mainly by hydrogen bonds, van der Waals forces, and electrostatic interactions. The release behavior of API is highly dependent on the physicochemical properties of mesoporous carbons. The release rate of APIs could be regulated by the introduction of functional groups and by changing the pH of the receptor medium. Acknowledgments—This research was supported by the National Science Centre, Poland (project SONATA-12 no: 2016/23/D/NZ7/01347).Keywords: ordered mesoporous carbons, sorption capacity, drug delivery, carbon nanocarriers
Procedia PDF Downloads 17427 Index and Mechanical Geotechnical Properties and Their Control on the Strength and Durability of the Cainozoic Calcarenites in KwaZulu-Natal, South Africa
Authors: Luvuno N. Jele, Warwick W. Hastie, Andrew Green
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Calcarenite is a clastic sedimentary beach rock composed of more than 50% sand sized (0.0625 – 2 mm) carbonate grains. In South Africa, these rocks occur as a narrow belt along most of the coast of KwaZulu-Natal and sporadically along the coast of the Eastern Cape. Calcarenites contain a high percentage of calcium carbonate, and due to a number of its physical and structural features, like porosity, cementing material, sedimentary structures, grain shape, and grain size; they are more prone to chemical and mechanical weathering. The objective of the research is to study the strength and compressibility characteristics of the calcarenites along the coast of KwaZulu-Natal to be able to better understand the geotechnical behaviour of these rocks, which may help to predict areas along the coast which may be potentially susceptible to failure/differential settling resulting in damage to property. A total of 148 cores were prepared and analyzed. Cores were analyzed perpendicular and parallel to bedding. Tests were carried out in accordance with the relevant codes and recommendations of the International Society for Rock Mechanics, American Standard Testing Methods, and Committee of Land and Transport Standard Specifications for Road and Bridge Works for State Road Authorities. Test carried out included: x-ray diffraction, petrography, shape preferred orientation (SPO), 3-D Tomography, rock porosity, rock permeability, ethylene glycol, slake durability, rock water absorption, Duncan swelling index, triaxial compressive strength, Brazilian tensile strength and uniaxial compression test with elastic modulus. The beach-rocks have a uniaxial compressive strength (UCS) ranging from 17,84Mpa to 287,35Mpa and exhibit three types of failure; (1) single sliding shear failure, (2) complete cone development, and (3) splitting failure. Brazilian tensile strength of the rocks ranges from 2.56 Mpa to 12,40 Ma, with those tested perpendicular to bedding showing lower tensile strength. Triaxial compressive tests indicate calcarenites have strength ranging from 86,10 Mpa to 371,85 Mpa. Common failure mode in the triaxial test is a single sliding shear failure. Porosity of the rocks varies from 1.25 % to 26.52 %. Rock tests indicate that the direction of loading, whether it be parallel to bedding or perpendicular to bedding, plays no significantrole in the strength and durability of the calcarenites. Porosity, cement type, and grain texture play major roles.UCS results indicate that saturated cores are weaker in strength compared to dry samples. Thus, water or moisture content plays a significant role in the strength and durability of the beach-rock. Loosely packed, highly porous and low magnesian-calcite bearing calcarenites show a decrease in strength compared to the densely packed, low porosity and high magnesian-calcite bearing calcarenites.Keywords: beach-rock, calcarenite, cement, compressive, failure, porosity, strength, tensile, grains
Procedia PDF Downloads 9226 Ectopic Osteoinduction of Porous Composite Scaffolds Reinforced with Graphene Oxide and Hydroxyapatite Gradient Density
Authors: G. M. Vlasceanu, H. Iovu, E. Vasile, M. Ionita
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Herein, the synthesis and characterization of chitosan-gelatin highly porous scaffold reinforced with graphene oxide, and hydroxyapatite (HAp), crosslinked with genipin was targeted. In tissue engineering, chitosan and gelatin are two of the most robust biopolymers with wide applicability due to intrinsic biocompatibility, biodegradability, low antigenicity properties, affordability, and ease of processing. HAp, per its exceptional activity in tuning cell-matrix interactions, is acknowledged for its capability of sustaining cellular proliferation by promoting bone-like native micro-media for cell adjustment. Genipin is regarded as a top class cross-linker, while graphene oxide (GO) is viewed as one of the most performant and versatile fillers. The composites with natural bone HAp/biopolymer ratio were obtained by cascading sonochemical treatments, followed by uncomplicated casting methods and by freeze-drying. Their structure was characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction, while overall morphology was investigated by Scanning Electron Microscopy (SEM) and micro-Computer Tomography (µ-CT). Ensuing that, in vitro enzyme degradation was performed to detect the most promising compositions for the development of in vivo assays. Suitable GO dispersion was ascertained within the biopolymer mix as nanolayers specific signals lack in both FTIR and XRD spectra, and the specific spectral features of the polymers persisted with GO load enhancement. Overall, correlations between the GO induced material structuration, crystallinity variations, and chemical interaction of the compounds can be correlated with the physical features and bioactivity of each composite formulation. Moreover, the HAp distribution within follows an auspicious density gradient tuned for hybrid osseous/cartilage matter architectures, which were mirrored in the mice model tests. Hence, the synthesis route of a natural polymer blend/hydroxyapatite-graphene oxide composite material is anticipated to emerge as influential formulation in bone tissue engineering. Acknowledgement: This work was supported by the project 'Work-based learning systems using entrepreneurship grants for doctoral and post-doctoral students' (Sisteme de invatare bazate pe munca prin burse antreprenor pentru doctoranzi si postdoctoranzi) - SIMBA, SMIS code 124705 and by a grant of the National Authority for Scientific Research and Innovation, Operational Program Competitiveness Axis 1 - Section E, Program co-financed from European Regional Development Fund 'Investments for your future' under the project number 154/25.11.2016, P_37_221/2015. The nano-CT experiments were possible due to European Regional Development Fund through Competitiveness Operational Program 2014-2020, Priority axis 1, ID P_36_611, MySMIS code 107066, INOVABIOMED.Keywords: biopolymer blend, ectopic osteoinduction, graphene oxide composite, hydroxyapatite
Procedia PDF Downloads 10325 Structural Characterization and Hot Deformation Behaviour of Al3Ni2/Al3Ni in-situ Core-shell intermetallic in Al-4Cu-Ni Composite
Authors: Ganesh V., Asit Kumar Khanra
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An in-situ powder metallurgy technique was employed to create Ni-Al3Ni/Al3Ni2 core-shell-shaped aluminum-based intermetallic reinforced composites. The impact of Ni addition on the phase composition, microstructure, and mechanical characteristics of the Al-4Cu-xNi (x = 0, 2, 4, 6, 8, 10 wt.%) in relation to various sintering temperatures was investigated. Microstructure evolution was extensively examined using X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), and transmission electron microscopy (TEM) techniques. Initially, under sintering conditions, the formation of "Single Core-Shell" structures was observed, consisting of Ni as the core with Al3Ni2 intermetallic, whereas samples sintered at 620°C exhibited both "Single Core-Shell" and "Double Core-Shell" structures containing Al3Ni2 and Al3Ni intermetallics formed between the Al matrix and Ni reinforcements. The composite achieved a high compressive yield strength of 198.13 MPa and ultimate strength of 410.68 MPa, with 24% total elongation for the sample containing 10 wt.% Ni. Additionally, there was a substantial increase in hardness, reaching 124.21 HV, which is 2.4 times higher than that of the base aluminum. Nanoindentation studies showed hardness values of 1.54, 4.65, 21.01, 13.16, 5.52, 6.27, and 8.39GPa corresponding to α-Al matrix, Ni, Al3Ni2, Ni and Al3Ni2 interface, Al3Ni, and their respective interfaces. Even at 200°C, it retained 54% of its room temperature strength (90.51 MPa). To investigate the deformation behavior of the composite material, experiments were conducted at deformation temperatures ranging from 300°C to 500°C, with strain rates varying from 0.0001s-1 to 0.1s-1. A sine-hyperbolic constitutive equation was developed to characterize the flow stress of the composite, which exhibited a significantly higher hot deformation activation energy of 231.44 kJ/mol compared to the self-diffusion of pure aluminum. The formation of Al2Cu intermetallics at grain boundaries and Al3Ni2/Al3Ni within the matrix hindered dislocation movement, leading to an increase in activation energy, which might have an adverse effect on high-temperature applications. Two models, the Strain-compensated Arrhenius model and the Artificial Neural Network (ANN) model, were developed to predict the composite's flow behavior. The ANN model outperformed the Strain-compensated Arrhenius model with a lower average absolute relative error of 2.266%, a smaller root means square error of 1.2488 MPa, and a higher correlation coefficient of 0.9997. Processing maps revealed that the optimal hot working conditions for the composite were in the temperature range of 420-500°C and strain rates between 0.0001s-1 and 0.001s-1. The changes in the composite microstructure were successfully correlated with the theory of processing maps, considering temperature and strain rate conditions. The uneven distribution in the shape and size of Core-shell/Al3Ni intermetallic compounds influenced the flow stress curves, leading to Dynamic Recrystallization (DRX), followed by partial Dynamic Recovery (DRV), and ultimately strain hardening. This composite material shows promise for applications in the automobile and aerospace industries.Keywords: core-shell structure, hot deformation, intermetallic compounds, powder metallurgy
Procedia PDF Downloads 1724 Tailoring Structural, Thermal and Luminescent Properties of Solid-State MIL-53(Al) MOF via Fe³⁺ Cation Exchange
Authors: T. Ul Rehman, S. Agnello, F. M. Gelardi, M. M. Calvino, G. Lazzara, G. Buscarino, M. Cannas
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Metal-Organic Frameworks (MOFs) have emerged as promising candidates for detecting metal ions owing to their large surface area, customizable porosity, and diverse functionalities. In recent years, there has been a surge in research focused on MOFs with luminescent properties. These frameworks are constructed through coordinated bonding between metal ions and multi-dentate ligands, resulting in inherent fluorescent structures. Their luminescent behavior is influenced by factors like structural composition, surface morphology, pore volume, and interactions with target analytes, particularly metal ions. MOFs exhibit various sensing mechanisms, including photo-induced electron transfer (PET) and charge transfer processes such as ligand-to-metal (LMCT) and metal-to-ligand (MLCT) transitions. Among these, MIL-53(Al) stands out due to its flexibility, stability, and specific affinity towards certain metal ions, making it a promising platform for selective metal ion sensing. This study investigates the structural, thermal, and luminescent properties of MIL-53(Al) metal-organic framework (MOF) upon Fe3+ cation exchange. Two separate sets of samples were prepared to activate the MOF powder at different temperatures. The first set of samples, referred to as MIL-53(Al), activated (120°C), was prepared by activating the raw powder in a glass tube at 120°C for 12 hours and then sealing it. The second set of samples, referred to as MIL-53(Al), activated (300°C), was prepared by activating the MIL-53(Al) powder in a glass tube at 300°C for 70 hours. Additionally, 25 mg of MIL-53(Al) powder was dispersed in 5 mL of Fe3+ solution at various concentrations (0.1-100 mM) for the cation exchange experiment. The suspension was centrifuged for five minutes at 10,000 rpm to extract MIL-53(Al) powder. After three rounds of washing with ultrapure water, MIL-53(Al) powder was heated at 120°C for 12 hours. For PXRD and TGA analyses, a sample of the obtained MIL-53(Al) was used. We also activated the cation-exchanged samples for time-resolved photoluminescence (TRPL) measurements at two distinct temperatures (120 and 300°C) for comparative analysis. Powder X-ray diffraction patterns reveal amorphization in samples with higher Fe3+ concentrations, attributed to alterations in coordination environments and ion exchange dynamics. Thermal decomposition analysis shows reduced weight loss in Fe3+-exchanged MOFs, indicating enhanced stability due to stronger metal-ligand bonds and altered decomposition pathways. Raman spectroscopy demonstrates intensity decrease, shape disruption, and frequency shifts, indicative of structural perturbations induced by cation exchange. Photoluminescence spectra exhibit ligand-based emission (π-π* or n-π*) and ligand-to-metal charge transfer (LMCT), influenced by activation temperature and Fe3+ incorporation. Quenching of luminescence intensity and shorter lifetimes upon Fe3+ exchange result from structural distortions and Fe3+ binding to organic linkers. In a nutshell, this research underscores the complex interplay between composition, structure, and properties in MOFs, offering insights into their potential for diverse applications in catalysis, gas storage, and luminescent devices.Keywords: Fe³⁺ cation exchange, luminescent metal-organic frameworks (LMOFs), MIL-53(Al), solid-state analysis
Procedia PDF Downloads 6423 Synchrotron Based Techniques for the Characterization of Chemical Vapour Deposition Overgrowth Diamond Layers on High Pressure, High Temperature Substrates
Authors: T. N. Tran Thi, J. Morse, C. Detlefs, P. K. Cook, C. Yıldırım, A. C. Jakobsen, T. Zhou, J. Hartwig, V. Zurbig, D. Caliste, B. Fernandez, D. Eon, O. Loto, M. L. Hicks, A. Pakpour-Tabrizi, J. Baruchel
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The ability to grow boron-doped diamond epilayers of high crystalline quality is a prerequisite for the fabrication of diamond power electronic devices, in particular high voltage diodes and metal-oxide-semiconductor (MOS) transistors. Boron and intrinsic diamond layers are homoepitaxially overgrown by microwave assisted chemical vapour deposition (MWCVD) on single crystal high pressure, high temperature (HPHT) grown bulk diamond substrates. Various epilayer thicknesses were grown, with dopant concentrations ranging from 1021 atom/cm³ at nanometer thickness in the case of 'delta doping', up 1016 atom/cm³ and 50µm thickness or high electric field drift regions. The crystalline quality of these overgrown layers as regards defects, strain, distortion… is critical for the device performance through its relation to the final electrical properties (Hall mobility, breakdown voltage...). In addition to the optimization of the epilayer growth conditions in the MWCVD reactor, other important questions related to the crystalline quality of the overgrown layer(s) are: 1) what is the dependence on the bulk quality and surface preparation methods of the HPHT diamond substrate? 2) how do defects already present in the substrate crystal propagate into the overgrown layer; 3) what types of new defects are created during overgrowth, what are their growth mechanisms, and how can these defects be avoided? 4) how can we relate in a quantitative manner parameters related to the measured crystalline quality of the boron doped layer to the electronic properties of final processed devices? We describe synchrotron-based techniques developed to address these questions. These techniques allow the visualization of local defects and crystal distortion which complements the data obtained by other well-established analysis methods such as AFM, SIMS, Hall conductivity…. We have used Grazing Incidence X-ray Diffraction (GIXRD) at the ID01 beamline of the ESRF to study lattice parameters and damage (strain, tilt and mosaic spread) both in diamond substrate near surface layers and in thick (10–50 µm) overgrown boron doped diamond epi-layers. Micro- and nano-section topography have been carried out at both the BM05 and ID06-ESRF) beamlines using rocking curve imaging techniques to study defects which have propagated from the substrate into the overgrown layer(s) and their influence on final electronic device performance. These studies were performed using various commercially sourced HPHT grown diamond substrates, with the MWCVD overgrowth carried out at the Fraunhofer IAF-Germany. The synchrotron results are in good agreement with low-temperature (5°K) cathodoluminescence spectroscopy carried out on the grown samples using an Inspect F5O FESEM fitted with an IHR spectrometer.Keywords: synchrotron X-ray diffaction, crystalline quality, defects, diamond overgrowth, rocking curve imaging
Procedia PDF Downloads 25922 Inverse Problem Method for Microwave Intrabody Medical Imaging
Authors: J. Chamorro-Servent, S. Tassani, M. A. Gonzalez-Ballester, L. J. Roca, J. Romeu, O. Camara
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Electromagnetic and microwave imaging (MWI) have been used in medical imaging in the last years, being the most common applications of breast cancer and stroke detection or monitoring. In those applications, the subject or zone to observe is surrounded by a number of antennas, and the Nyquist criterium can be satisfied. Additionally, the space between the antennas (transmitting and receiving the electromagnetic fields) and the zone to study can be prepared in a homogeneous scenario. However, this may differ in other cases as could be intracardiac catheters, stomach monitoring devices, pelvic organ systems, liver ablation monitoring devices, or uterine fibroids’ ablation systems. In this work, we analyzed different MWI algorithms to find the most suitable method for dealing with an intrabody scenario. Due to the space limitations usually confronted on those applications, the device would have a cylindrical configuration of a maximum of eight transmitters and eight receiver antennas. This together with the positioning of the supposed device inside a body tract impose additional constraints in order to choose a reconstruction method; for instance, it inhabitants the use of well-known algorithms such as filtered backpropagation for diffraction tomography (due to the unusual configuration with probes enclosed by the imaging region). Finally, the difficulty of simulating a realistic non-homogeneous background inside the body (due to the incomplete knowledge of the dielectric properties of other tissues between the antennas’ position and the zone to observe), also prevents the use of Born and Rytov algorithms due to their limitations with a heterogeneous background. Instead, we decided to use a time-reversed algorithm (mostly used in geophysics) due to its characteristics of ignoring heterogeneities in the background medium, and of focusing its generated field onto the scatters. Therefore, a 2D time-reversed finite difference time domain was developed based on the time-reversed approach for microwave breast cancer detection. Simultaneously an in-silico testbed was also developed to compare ground-truth dielectric properties with corresponding microwave imaging reconstruction. Forward and inverse problems were computed varying: the frequency used related to a small zone to observe (7, 7.5 and 8 GHz); a small polyp diameter (5, 7 and 10 mm); two polyp positions with respect to the closest antenna (aligned or disaligned); and the (transmitters-to-receivers) antenna combination used for the reconstruction (1-1, 8-1, 8-8 or 8-3). Results indicate that when using the existent time-reversed method for breast cancer here for the different combinations of transmitters and receivers, we found false positives due to the high degrees of freedom and unusual configuration (and the possible violation of Nyquist criterium). Those false positives founded in 8-1 and 8-8 combinations, highly reduced with the 1-1 and 8-3 combination, being the 8-3 configuration de most suitable (three neighboring receivers at each time). The 8-3 configuration creates a region-of-interest reduced problem, decreasing the ill-posedness of the inverse problem. To conclude, the proposed algorithm solves the main limitations of the described intrabody application, successfully detecting the angular position of targets inside the body tract.Keywords: FDTD, time-reversed, medical imaging, microwave imaging
Procedia PDF Downloads 12521 Zinc Oxide Varistor Performance: A 3D Network Model
Authors: Benjamin Kaufmann, Michael Hofstätter, Nadine Raidl, Peter Supancic
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ZnO varistors are the leading overvoltage protection elements in today’s electronic industry. Their highly non-linear current-voltage characteristics, very fast response times, good reliability and attractive cost of production are unique in this field. There are challenges and questions unsolved. Especially, the urge to create even smaller, versatile and reliable parts, that fit industry’s demands, brings manufacturers to the limits of their abilities. Although, the varistor effect of sintered ZnO is known since the 1960’s, and a lot of work was done on this field to explain the sudden exponential increase of conductivity, the strict dependency on sinter parameters, as well as the influence of the complex microstructure, is not sufficiently understood. For further enhancement and down-scaling of varistors, a better understanding of the microscopic processes is needed. This work attempts a microscopic approach to investigate ZnO varistor performance. In order to cope with the polycrystalline varistor ceramic and in order to account for all possible current paths through the material, a preferably realistic model of the microstructure was set up in the form of three-dimensional networks where every grain has a constant electric potential, and voltage drop occurs only at the grain boundaries. The electro-thermal workload, depending on different grain size distributions, was investigated as well as the influence of the metal-semiconductor contact between the electrodes and the ZnO grains. A number of experimental methods are used, firstly, to feed the simulations with realistic parameters and, secondly, to verify the obtained results. These methods are: a micro 4-point probes method system (M4PPS) to investigate the current-voltage characteristics between single ZnO grains and between ZnO grains and the metal electrode inside the varistor, micro lock-in infrared thermography (MLIRT) to detect current paths, electron back scattering diffraction and piezoresponse force microscopy to determine grain orientations, atom probe to determine atomic substituents, Kelvin probe force microscopy for investigating grain surface potentials. The simulations showed that, within a critical voltage range, the current flow is localized along paths which represent only a tiny part of the available volume. This effect could be observed via MLIRT. Furthermore, the simulations exhibit that the electric power density, which is inversely proportional to the number of active current paths, since this number determines the electrical active volume, is dependent on the grain size distribution. M4PPS measurements showed that the electrode-grain contacts behave like Schottky diodes and are crucial for asymmetric current path development. Furthermore, evaluation of actual data suggests that current flow is influenced by grain orientations. The present results deepen the knowledge of influencing microscopic factors on ZnO varistor performance and can give some recommendations on fabrication for obtaining more reliable ZnO varistors.Keywords: metal-semiconductor contact, Schottky diode, varistor, zinc oxide
Procedia PDF Downloads 28120 Active Filtration of Phosphorus in Ca-Rich Hydrated Oil Shale Ash Filters: The Effect of Organic Loading and Form of Precipitated Phosphatic Material
Authors: Päärn Paiste, Margit Kõiv, Riho Mõtlep, Kalle Kirsimäe
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For small-scale wastewater management, the treatment wetlands (TWs) as a low cost alternative to conventional treatment facilities, can be used. However, P removal capacity of TW systems is usually problematic. P removal in TWs is mainly dependent on the physico–chemical and hydrological properties of the filter material. Highest P removal efficiency has been shown trough Ca-phosphate precipitation (i.e. active filtration) in Ca-rich alkaline filter materials, e.g. industrial by-products like hydrated oil shale ash (HOSA), metallurgical slags. In this contribution we report preliminary results of a full-scale TW system using HOSA material for P removal for a municipal wastewater at Nõo site, Estonia. The main goals of this ongoing project are to evaluate: a) the long-term P removal efficiency of HOSA using real waste water; b) the effect of high organic loading rate; c) variable P-loading effects on the P removal mechanism (adsorption/direct precipitation); and d) the form and composition of phosphate precipitates. Onsite full-scale experiment with two concurrent filter systems for treatment of municipal wastewater was established in September 2013. System’s pretreatment steps include septic tank (2 m2) and vertical down-flow LECA filters (3 m2 each), followed by horizontal subsurface HOSA filters (effective volume 8 m3 each). Overall organic and hydraulic loading rates of both systems are the same. However, the first system is operated in a stable hydraulic loading regime and the second in variable loading regime that imitates the wastewater production in an average household. Piezometers for water and perforated sample containers for filter material sampling were incorporated inside the filter beds to allow for continuous in-situ monitoring. During the 18 months of operation the median removal efficiency (inflow to outflow) of both systems were over 99% for TP, 93% for COD and 57% for TN. However, we observed significant differences in the samples collected in different points inside the filter systems. In both systems, we observed development of preferred flow paths and zones with high and low loadings. The filters show formation and a gradual advance of a “dead” zone along the flow path (zone with saturated filter material characterized by ineffective removal rates), which develops more rapidly in the system working under variable loading regime. The formation of the “dead” zone is accompanied by the growth of organic substances on the filter material particles that evidently inhibit the P removal. Phase analysis of used filter materials using X-ray diffraction method reveals formation of minor amounts of amorphous Ca-phosphate precipitates. This finding is supported by ATR-FTIR and SEM-EDS measurements, which also reveal Ca-phosphate and authigenic carbonate precipitation. Our first experimental results demonstrate that organic pollution and loading regime significantly affect the performance of hydrated ash filters. The material analyses also show that P is incorporated into a carbonate substituted hydroxyapatite phase.Keywords: active filtration, apatite, hydrated oil shale ash, organic pollution, phosphorus
Procedia PDF Downloads 27219 Functional Plasma-Spray Ceramic Coatings for Corrosion Protection of RAFM Steels in Fusion Energy Systems
Authors: Chen Jiang, Eric Jordan, Maurice Gell, Balakrishnan Nair
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Nuclear fusion, one of the most promising options for reliably generating large amounts of carbon-free energy in the future, has seen a plethora of ground-breaking technological advances in recent years. An efficient and durable “breeding blanket”, needed to ensure a reactor’s self-sufficiency by maintaining the optimal coolant temperature as well as by minimizing radiation dosage behind the blanket, still remains a technological challenge for the various reactor designs for commercial fusion power plants. A relatively new dual-coolant lead-lithium (DCLL) breeder design has exhibited great potential for high-temperature (>700oC), high-thermal-efficiency (>40%) fusion reactor operation. However, the structural material, namely reduced activation ferritic-martensitic (RAFM) steel, is not chemically stable in contact with molten Pb-17%Li coolant. Thus, to utilize this new promising reactor design, the demand for effective corrosion-resistant coatings on RAFM steels represents a pressing need. Solution Spray Technologies LLC (SST) is developing a double-layer ceramic coating design to address the corrosion protection of RAFM steels, using a novel solution and solution/suspension plasma spray technology through a US Department of Energy-funded project. Plasma spray is a coating deposition method widely used in many energy applications. Novel derivatives of the conventional powder plasma spray process, known as the solution-precursor and solution/suspension-hybrid plasma spray process, are powerful methods to fabricate thin, dense ceramic coatings with complex compositions necessary for the corrosion protection in DCLL breeders. These processes can be used to produce ultra-fine molten splats and to allow fine adjustment of coating chemistry. Thin, dense ceramic coatings with chosen chemistry for superior chemical stability in molten Pb-Li, low activation properties, and good radiation tolerance, is ideal for corrosion-protection of RAFM steels. A key challenge is to accommodate its CTE mismatch with the RAFM substrate through the selection and incorporation of appropriate bond layers, thus allowing for enhanced coating durability and robustness. Systematic process optimization is being used to define the optimal plasma spray conditions for both the topcoat and bond-layer, and X-ray diffraction and SEM-EDS are applied to successfully validate the chemistry and phase composition of the coatings. The plasma-sprayed double-layer corrosion resistant coatings were also deposited onto simulated RAFM steel substrates, which are being tested separately under thermal cycling, high-temperature moist air oxidation as well as molten Pb-Li capsule corrosion conditions. Results from this testing on coated samples, and comparisons with bare RAFM reference samples will be presented and conclusions will be presented assessing the viability of the new ceramic coatings to be viable corrosion prevention systems for DCLL breeders in commercial nuclear fusion reactors.Keywords: breeding blanket, corrosion protection, coating, plasma spray
Procedia PDF Downloads 30618 Digital Holographic Interferometric Microscopy for the Testing of Micro-Optics
Authors: Varun Kumar, Chandra Shakher
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Micro-optical components such as microlenses and microlens array have numerous engineering and industrial applications for collimation of laser diodes, imaging devices for sensor system (CCD/CMOS, document copier machines etc.), for making beam homogeneous for high power lasers, a critical component in Shack-Hartmann sensor, fiber optic coupling and optical switching in communication technology. Also micro-optical components have become an alternative for applications where miniaturization, reduction of alignment and packaging cost are necessary. The compliance with high-quality standards in the manufacturing of micro-optical components is a precondition to be compatible on worldwide markets. Therefore, high demands are put on quality assurance. For quality assurance of these lenses, an economical measurement technique is needed. For cost and time reason, technique should be fast, simple (for production reason), and robust with high resolution. The technique should provide non contact, non-invasive and full field information about the shape of micro- optical component under test. The interferometric techniques are noncontact type and non invasive and provide full field information about the shape of the optical components. The conventional interferometric technique such as holographic interferometry or Mach-Zehnder interferometry is available for characterization of micro-lenses. However, these techniques need more experimental efforts and are also time consuming. Digital holography (DH) overcomes the above described problems. Digital holographic microscopy (DHM) allows one to extract both the amplitude and phase information of a wavefront transmitted through the transparent object (microlens or microlens array) from a single recorded digital hologram by using numerical methods. Also one can reconstruct the complex object wavefront at different depths due to numerical reconstruction. Digital holography provides axial resolution in nanometer range while lateral resolution is limited by diffraction and the size of the sensor. In this paper, Mach-Zehnder based digital holographic interferometric microscope (DHIM) system is used for the testing of transparent microlenses. The advantage of using the DHIM is that the distortions due to aberrations in the optical system are avoided by the interferometric comparison of reconstructed phase with and without the object (microlens array). In the experiment, first a digital hologram is recorded in the absence of sample (microlens array) as a reference hologram. Second hologram is recorded in the presence of microlens array. The presence of transparent microlens array will induce a phase change in the transmitted laser light. Complex amplitude of object wavefront in presence and absence of microlens array is reconstructed by using Fresnel reconstruction method. From the reconstructed complex amplitude, one can evaluate the phase of object wave in presence and absence of microlens array. Phase difference between the two states of object wave will provide the information about the optical path length change due to the shape of the microlens. By the knowledge of the value of the refractive index of microlens array material and air, the surface profile of microlens array is evaluated. The Sag of microlens and radius of curvature of microlens are evaluated and reported. The sag of microlens agrees well within the experimental limit as provided in the specification by the manufacturer.Keywords: micro-optics, microlens array, phase map, digital holographic interferometric microscopy
Procedia PDF Downloads 49717 Molecular Characterization and Arsenic Mobilization Properties of a Novel Strain IIIJ3-1 Isolated from Arsenic Contaminated Aquifers of Brahmaputra River Basin, India
Authors: Soma Ghosh, Balaram Mohapatra, Pinaki Sar, Abhijeet Mukherjee
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Microbial role in arsenic (As) mobilization in the groundwater aquifers of Brahmaputra river basin (BRB) in India, severely threatened by high concentrations of As, remains largely unknown. The present study, therefore, is a molecular and ecophysiological characterization of an indigenous bacterium strain IIIJ3-1 isolated from As contaminated groundwater of BRB and application of this strain in several microcosm set ups differing in their organic carbon (OC) source and terminal electron acceptors (TEA), to understand its role in As dissolution under aerobic and anaerobic conditions. Strain IIIJ3-1 was found to be a new facultative anaerobic, gram-positive, endospore-forming strain capable of arsenite (As3+) oxidation and dissimilatory arsenate (As5+) reduction. The bacterium exhibited low genomic (G+C)% content (45 mol%). Although, its 16S rRNA gene sequence revealed a maximum similarity of 99% with Bacillus cereus ATCC 14579(T) but the DNA-DNA relatedness of their genomic DNAs was only 49.9%, which remains well below the value recommended to delimit different species. Abundance of fatty acids iC17:0, iC15:0 and menaquinone (MK) 7 though corroborates its taxonomic affiliation with B. cereus sensu-lato group, presence of hydroxy fatty acids (HFAs), C18:2, MK5 and MK6 marked its uniqueness. Besides being highly As resistant (MTC=10mM As3+, 350mM As5+), metabolically diverse, efficient aerobic As3+ oxidizer; it exhibited near complete dissimilatory reduction of As5+ (1 mM). Utilization of various carbon sources with As5+ as TEA revealed lactate to serve as the best electron donor. Aerobic biotransformation assay yielded a lower Km for As3+ oxidation than As5+ reduction. Arsenic homeostasis was found to be conferred by the presence of arr, arsB, aioB, and acr3(1) genes. Scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX) analysis of this bacterium revealed reduction in cell size upon exposure to As and formation of As-rich electron opaque dots following growth with As3+. Incubation of this strain with sediment (sterilised) collected from BRB aquifers under varying OC, TEA and redox conditions revealed that the strain caused highest As mobilization from solid to aqueous phase under anaerobic condition with lactate and nitrate as electron donor and acceptor, respectively. Co-release of highest concentrations of oxalic acid, a well known bioweathering agent, considerable fold increase in viable cell counts and SEM-EDX and X-ray diffraction analysis of the sediment after incubation under this condition indicated that As release is consequent to microbial bioweathering of the minerals. Co-release of other elements statistically proves decoupled release of As with Fe and Zn. Principle component analysis also revealed prominent role of nitrate under aerobic and/or anaerobic condition in As release by strain IIIJ3-1. This study, therefore, is the first to isolate, characterize and reveal As mobilization property of a strain belonging to the Bacillus cereus sensu lato group isolated from highly As contaminated aquifers of Brahmaputra River Basin.Keywords: anaerobic microcosm, arsenic rich electron opaque dots, Arsenic release, Bacillus strain IIIJ3-1
Procedia PDF Downloads 12516 Synthesis by Mechanical Alloying and Characterization of FeNi₃ Nanoalloys
Authors: Ece A. Irmak, Amdulla O. Mekhrabov, M. Vedat Akdeniz
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There is a growing interest on the synthesis and characterization of nanoalloys since the unique chemical, and physical properties of nanoalloys can be tuned and, consequently, new structural motifs can be created by varying the type of constituent elements, atomic and magnetic ordering, as well as size and shape of the nanoparticles. Due to the fine size effects, magnetic nanoalloys have considerable attention with their enhanced mechanical, electrical, optical and magnetic behavior. As an important magnetic nanoalloy, the novel application area of Fe-Ni based nanoalloys is expected to be widened in the chemical, aerospace industry and magnetic biomedical applications. Noble metals have been using in biomedical applications for several years because of their surface plasmon properties. In this respect, iron-nickel nanoalloys are promising materials for magnetic biomedical applications because they show novel properties such as superparamagnetism and surface plasmon resonance property. Also, there is great attention for the usage Fe-Ni based nanoalloys as radar absorbing materials in aerospace and stealth industry due to having high Curie temperature, high permeability and high saturation magnetization with good thermal stability. In this study, FeNi₃ bimetallic nanoalloys were synthesized by mechanical alloying in a planetary high energy ball mill. In mechanical alloying, micron size powders are placed into the mill with milling media. The powders are repeatedly deformed, fractured and alloyed by high energy collision under the impact of balls until the desired composition and particle size is achieved. The experimental studies were carried out in two parts. Firstly, dry mechanical alloying with high energy dry planetary ball milling was applied to obtain FeNi₃ nanoparticles. Secondly, dry milling was followed by surfactant-assisted ball milling to observe the surfactant and solvent effect on the structure, size, and properties of the FeNi₃ nanoalloys. In the first part, the powder sample of iron-nickel was prepared according to the 1:3 iron to nickel ratio to produce FeNi₃ nanoparticles and the 1:10 powder to ball weight ratio. To avoid oxidation during milling, the vials had been filled with Ar inert gas before milling started. The powders were milled for 80 hours in total and the synthesis of the FeNi₃ intermetallic nanoparticles was succeeded by mechanical alloying in 40 hours. Also, regarding the particle size, it was found that the amount of nano-sized particles raised with increasing milling time. In the second part of the study, dry milling of the Fe and Ni powders with the same stoichiometric ratio was repeated. Then, to prevent agglomeration and to obtain smaller sized nanoparticles with superparamagnetic behavior, surfactants and solvent are added to the system, after 40-hour milling time, with the completion of the mechanical alloying. During surfactant-assisted ball milling, heptane was used as milling medium, and as surfactants, oleic acid and oleylamine were used in the high energy ball milling processes. The characterization of the alloyed particles in terms of microstructure, morphology, particle size, thermal and magnetic properties with respect to milling time was done by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, vibrating-sample magnetometer, and differential scanning calorimetry.Keywords: iron-nickel systems, magnetic nanoalloys, mechanical alloying, nanoalloy characterization, surfactant-assisted ball milling
Procedia PDF Downloads 17915 Reduction and Smelting of Magnetic Fraction Obtained by Magnetic-Gravimetric-Separation (MGS) of Electric Arc Furnace Dust
Authors: Sara Scolari, Davide Mombelli, Gianluca Dall'Osto, Jasna Kastivnik, Gašper Tavčar, Carlo Mapelli
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The EIT Raw Materials RIS-DustRec-II project aims to transform Electric Arc Furnace Dust (EAFD) into a valuable resource by overcoming the challenges associated with traditional recycling approaches. EAFD, a zinc-rich industrial by-product typically recycled by the Waelz process, contains complex oxides such as franklinite (ZnFe₂O₄), which hinder the efficient extraction of zinc, by also introducing other valuable elements (Fe, Ni, Cr, Cu, …) in the slag. The project aims to develop a multistage multidisciplinary approach to separate EAFD into two streams: a magnetic and non-magnetic one. In this paper the production of self-reducing briquettes from the magnetic stream of EAFD with a reducing agent, aiming to drive carbothermic reduction and recover iron as a usable alloy, was investigated. Research was focused on optimizing the magnetic and subsequent gravimetric separation (MGS) processes, followed by high-temperature smelting to evaluate reduction efficiency and phase separation. The characterization of selected two different raw EAFD samples and their magnetic-gravitational separation to isolate zinc- and iron-rich fractions was performed by X-ray diffraction and scanning electron microscope. The iron-enriched concentrates were then agglomerated into self-reducing briquettes by mixing them with either biochar (olive pomace pyrolyzed at 350 and 750°C and wood chips pyrolyzed at 750 °C) and a Cupola Furnace dust as reducing agents, combined with gelatinized corn starch as a binder. Cylindrical briquettes were produced and cured for 14 days to ensure structural integrity during subsequent thermal treatments. Smelting tests were carried out at 1400 °C in an inert argon atmosphere to assess the metallization efficiency and the separation between metal and slag phases. A carbon/oxides mass ratio of 0.262 (C/(ZnO+Fe₂O₃)) was used in these tests to maintain continuity with previous studies and to standardize reduction conditions. The magnetic and gravimetric separations effectively isolated zinc- and iron-enriched fractions, particularly for one of the two EAFD, where the concentration of Zn in the concentration fraction was reduced by 8 wt.% while Fe reached 45 wt.%. The reduction tests conducted at 1400 °C showed that the chosen carbon/oxides ratio was sufficient for the smelting of the reducible oxides within the briquettes. However, an important limitation became apparent: the amount of carbon, exceeding the stochiometric value, proved to be excessive for the effective coalescence of metal droplets, preventing clear metal-slag separation. To address this, further smelting tests were carried out in an air atmosphere rather than inert conditions to burn off excess carbon. This paper demonstrates the potential of controlled carbothermic reduction for EAFD recycling. By carefully optimizing the C/(ZnO+Fe₂O₃) ratio, the process can maximize metal recovery while achieving better separation of the metal and slag phases. This approach offers a promising alternative to traditional EAFD recycling methods, with further studies recommended to refine the parameters for industrial application.Keywords: biochars, electrical arc furnace dust, metallization, smelting
Procedia PDF Downloads 1214 Single Crystal Growth in Floating-Zone Method and Properties of Spin Ladders: Quantum Magnets
Authors: Rabindranath Bag, Surjeet Singh
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Materials in which the electrons are strongly correlated provide some of the most challenging and exciting problems in condensed matter physics today. After the discovery of high critical temperature superconductivity in layered or two-dimensional copper oxides, many physicists got attention in cuprates and it led to an upsurge of interest in the synthesis and physical properties of copper-oxide based material. The quest to understand superconducting mechanism in high-temperature cuprates, drew physicist’s attention to somewhat simpler compounds consisting of spin-chains or one-dimensional lattice of coupled spins. Low-dimensional quantum magnets are of huge contemporary interest in basic sciences as well emerging technologies such as quantum computing and quantum information theory, and heat management in microelectronic devices. Spin ladder is an example of quasi one-dimensional quantum magnets which provides a bridge between one and two dimensional materials. One of the examples of quasi one-dimensional spin-ladder compounds is Sr14Cu24O41, which exhibits a lot of interesting and exciting physical phenomena in low dimensional systems. Very recently, the ladder compound Sr14Cu24O41 was shown to exhibit long-distance quantum entanglement crucial to quantum information theory. Also, it is well known that hole-compensation in this material results in very high (metal-like) anisotropic thermal conductivity at room temperature. These observations suggest that Sr14Cu24O41 is a potential multifunctional material which invites further detailed investigations. To investigate these properties one must needs a large and high quality of single crystal. But these systems are showing incongruently melting behavior, which brings many difficulties to grow a large and quality of single crystals. Hence, we are using TSFZ (Travelling Solvent Floating Zone) method to grow the high quality of single crystals of the low dimensional magnets. Apart from this, it has unique crystal structure (alternating stacks of plane containing edge-sharing CuO2 chains, and the plane containing two-leg Cu2O3 ladder with intermediate Sr layers along the b- axis), which is also incommensurate in nature. It exhibits abundant physical phenomenon such as spin dimerization, crystallization of charge holes and charge density wave. The maximum focus of research so far involved in introducing defects on A-site (Sr). However, apart from the A-site (Sr) doping, there are only few studies in which the B-site (Cu) doping of polycrystalline Sr14Cu24O41 have been discussed and the reason behind this is the possibility of two doping sites for Cu (CuO2 chain and Cu2O3 ladder). Therefore, in our present work, the crystals (pristine and Cu-site doped) were grown by using TSFZ method by tuning the growth parameters. The Laue diffraction images, optical polarized microscopy and Scanning Electron Microscopy (SEM) images confirm the quality of the grown crystals. Here, we report the single crystal growth, magnetic and transport properties of Sr14Cu24O41 and its lightly doped variants (magnetic and non-magnetic) containing less than 1% of Co, Ni, Al and Zn impurities. Since, any real system will have some amount of weak disorder, our studies on these ladder compounds with controlled dilute disorder would be significant in the present context.Keywords: low-dimensional quantum magnets, single crystal, spin-ladder, TSFZ technique
Procedia PDF Downloads 27313 Biosynthesis of a Nanoparticle-Antibody Phthalocyanine Photosensitizer for Use in Targeted Photodynamic Therapy of Cervical Cancer
Authors: Elvin P. Chizenga, Heidi Abrahamse
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Cancer cell resistance to therapy is the main cause of treatment failures and the poor prognosis of cancer convalescence. The progression of cervical cancer to other parts of the genitourinary system and the reported recurrence rates are overwhelming. Current treatments, including surgery, chemo and radiation have been inefficient in eradicating the tumor cells. These treatments are also associated with poor prognosis and reduced quality of life, including fertility loss. This has inspired the need for the development of new treatment modalities to eradicate cervical cancer successfully. Photodynamic Therapy (PDT) is a modern treatment modality that induces cell death by photochemical interactions of light and a photosensitizer, which in the presence of molecular oxygen, yields a set of chemical reactions that generate Reactive Oxygen Species (ROS) and other free radical species causing cell damage. Enhancing PDT using modified drug delivery can increase the concentration of the photosensitizer in the tumor cells, and this has the potential to maximize its therapeutic efficacy. In cervical cancer, all infected cells constitutively express genes of the E6 and E7 HPV viral oncoproteins, resulting in high concentrations of E6 and E7 in the cytoplasm. This provides an opportunity for active targeting of cervical cancer cells using immune-mediated drug delivery to maximize therapeutic efficacy. The use of nanoparticles in PDT has also proven effective in enhancing therapeutic efficacy. Gold nanoparticles (AuNps) in particular, are explored for their use in biomedicine due to their biocompatibility, low toxicity, and enhancement of drug uptake by tumor cells. In this present study, a biomolecule comprising of AuNPs, anti-E6 monoclonal antibodies, and Aluminium Phthalocyanine photosensitizer was synthesized for use in targeted PDT of cervical cancer. The AuNp-Anti-E6-Sulfonated Aluminium Phthalocyanine mix (AlPcSmix) photosensitizing biomolecule was synthesized by coupling AuNps and anti-E6 monoclonal antibodies to the AlPcSmix via Polyethylene Glycol (PEG) chemical links. The final product was characterized using Transmission Electron Microscope (TEM), Zeta Potential, Uv-Vis Spectrophotometry, Fourier Transform Infrared Spectroscopy (FTIR), and X-ray diffraction (XRD), to confirm its chemical structure and functionality. To observe its therapeutic role in treating cervical cancer, cervical cancer cells, HeLa cells were seeded in 3.4 cm² diameter culture dishes at a concentration of 5x10⁵ cells/ml, in vitro. The cells were treated with varying concentrations of the photosensitizing biomolecule and irradiated using a 673.2 nm wavelength of laser light. Post irradiation cellular responses were performed to observe changes in morphology, viability, proliferation, cytotoxicity, and cell death pathways induced. Dose-Dependent response of the cells to treatment was demonstrated as significant morphologic changes, increased cytotoxicity, and decreased cell viability and proliferation This study presented a synthetic biomolecule for targeted PDT of cervical cancer. The study suggested that PDT using this AuNp- Anti-E6- AlPcSmix photosensitizing biomolecule is a very effective treatment method for the eradication of cervical cancer cells, in vitro. Further studies in vivo need to be conducted to support the use of this biomolecule in treating cervical cancer in clinical settings.Keywords: anti-E6 monoclonal antibody, cervical cancer, gold nanoparticles, photodynamic therapy
Procedia PDF Downloads 12212 Effect of Thermal Treatment on Mechanical Properties of Reduced Activation Ferritic/Martensitic Eurofer Steel Grade
Authors: Athina Puype, Lorenzo Malerba, Nico De Wispelaere, Roumen Petrov, Jilt Sietsma
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Reduced activation ferritic/martensitic (RAFM) steels like EUROFER97 are primary candidate structural materials for first wall application in the future demonstration (DEMO) fusion reactor. Existing steels of this type obtain their functional properties by a two-stage heat treatment, which consists of an annealing stage at 980°C for thirty minutes followed by quenching and an additional tempering stage at 750°C for two hours. This thermal quench and temper (Q&T) treatment creates a microstructure of tempered martensite with, as main precipitates, M23C6 carbides, with M = Fe, Cr and carbonitrides of MX type, e.g. TaC and VN. The resulting microstructure determines the mechanical properties of the steel. The ductility is largely determined by the tempered martensite matrix, while the resistance to mechanical degradation, determined by the spatial and size distribution of precipitates and the martensite crystals, plays a key role in the high temperature properties of the steel. Unfortunately, the high temperature response of EUROFER97 is currently insufficient for long term use in fusion reactors, due to instability of the matrix phase and coarsening of the precipitates at prolonged high temperature exposure. The objective of this study is to induce grain refinement by appropriate modifications of the processing route in order to increase the high temperature strength of a lab-cast EUROFER RAFM steel grade. The goal of the work is to obtain improved mechanical behavior at elevated temperatures with respect to conventionally heat treated EUROFER97. A dilatometric study was conducted to study the effect of the annealing temperature on the mechanical properties after a Q&T treatment. The microstructural features were investigated with scanning electron microscopy (SEM), electron back-scattered diffraction (EBSD) and transmission electron microscopy (TEM). Additionally, hardness measurements, tensile tests at elevated temperatures and Charpy V-notch impact testing of KLST-type MCVN specimens were performed to study the mechanical properties of the furnace-heated lab-cast EUROFER RAFM steel grade. A significant prior austenite grain (PAG) refinement was obtained by lowering the annealing temperature of the conventionally used Q&T treatment for EUROFER97. The reduction of the PAG results in finer martensitic constituents upon quenching, which offers more nucleation sites for carbide and carbonitride formation upon tempering. The ductile-to-brittle transition temperature (DBTT) was found to decrease with decreasing martensitic block size. Additionally, an increased resistance against high temperature degradation was accomplished in the fine grained martensitic materials with smallest precipitates obtained by tailoring the annealing temperature of the Q&T treatment. It is concluded that the microstructural refinement has a pronounced effect on the DBTT without significant loss of strength and ductility. Further investigation into the optimization of the processing route is recommended to improve the mechanical behavior of RAFM steels at elevated temperatures.Keywords: ductile-to-brittle transition temperature (DBTT), EUROFER, reduced activation ferritic/martensitic (RAFM) steels, thermal treatments
Procedia PDF Downloads 29911 Enhancing Photocatalytic Activity of Oxygen Vacancies-Rich Tungsten Trioxide (WO₃) for Sustainable Energy Conversion and Water Purification
Authors: Satam Alotibi, Osama A. Hussein, Aziz H. Al-Shaibani, Nawaf A. Al-Aqeel, Abdellah Kaiba, Fatehia S. Alhakami, Mohammed Alyami, Talal F. Qahtan
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The demand for sustainable and efficient energy conversion using solar energy has grown rapidly in recent years. In this pursuit, solar-to-chemical conversion has emerged as a promising approach, with oxygen vacancies-rich tungsten trioxide (WO₃) playing a crucial role. This study presents a method for synthesizing oxygen vacancies-rich WO3, resulting in a significant enhancement of its photocatalytic activity, representing a significant step towards sustainable energy solutions. Experimental results underscore the importance of oxygen vacancies in modifying the properties of WO₃. These vacancies introduce additional energy states within the material, leading to a reduction in the bandgap, increased light absorption, and acting as electron traps, thereby reducing emissions. Our focus lies in developing oxygen vacancies-rich WO₃, which demonstrates unparalleled potential for improved photocatalytic applications. The effectiveness of oxygen vacancies-rich WO₃ in solar-to-chemical conversion was showcased through rigorous assessments of its photocatalytic degradation performance. Sunlight irradiation was employed to evaluate the material's effectiveness in degrading organic pollutants in wastewater. The results unequivocally demonstrate the superior photocatalytic performance of oxygen vacancies-rich WO₃ compared to conventional WO₃ nanomaterials, establishing its efficacy in sustainable and efficient energy conversion. Furthermore, the synthesized material is utilized to fabricate films, which are subsequently employed in immobilized WO₃ and oxygen vacancies-rich WO₃ reactors for water purification under natural sunlight irradiation. This application offers a sustainable and efficient solution for water treatment, harnessing solar energy for effective decontamination. In addition to investigating the photocatalytic capabilities, we extensively analyze the structural and chemical properties of the synthesized material. The synthesis process involves in situ thermal reduction of WO₃ nano-powder in a nitrogen environment, meticulously monitored using thermogravimetric analysis (TGA) to ensure precise control over the synthesis of oxygen vacancies-rich WO₃. Comprehensive characterization techniques such as UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), FTIR, Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) provide deep insights into the material's optical properties, chemical composition, elemental states, structure, surface properties, and crystalline structure. This study represents a significant advancement in sustainable energy conversion through solar-to-chemical processes and water purification. By harnessing the unique properties of oxygen vacancies-rich WO₃, we not only enhance our understanding of energy conversion mechanisms but also pave the way for the development of highly efficient and environmentally friendly photocatalytic materials. The application of this material in water purification demonstrates its versatility and potential to address critical environmental challenges. These findings bring us closer to a sustainable energy future and cleaner water resources, laying a solid foundation for a more sustainable planet.Keywords: sustainable energy conversion, solar-to-chemical conversion, oxygen vacancies-rich tungsten trioxide (WO₃), photocatalytic activity enhancement, water purification
Procedia PDF Downloads 6810 Impact of Air Pressure and Outlet Temperature on Physicochemical and Functional Properties of Spray-dried Skim Milk Powder
Authors: Adeline Meriaux, Claire Gaiani, Jennifer Burgain, Frantz Fournier, Lionel Muniglia, Jérémy Petit
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Spray-drying process is widely used for the production of dairy powders for food and pharmaceuticals industries. It involves the atomization of a liquid feed into fine droplets, which are subsequently dried through contact with a hot air flow. The resulting powders permit transportation cost reduction and shelf life increase but can also exhibit various interesting functionalities (flowability, solubility, protein modification or acid gelation), depending on operating conditions and milk composition. Indeed, particles porosity, surface composition, lactose crystallization, protein denaturation, protein association or crust formation may change. Links between spray-drying conditions and physicochemical and functional properties of powders were investigated by a design of experiment methodology and analyzed by principal component analysis. Quadratic models were developed, and multicriteria optimization was carried out by the use of genetic algorithm. At the time of abstract submission, verification spray-drying trials are ongoing. To perform experiments, milk from dairy farm was collected, skimmed, froze and spray-dried at different air pressure (between 1 and 3 bars) and outlet temperature (between 75 and 95 °C). Dry matter, minerals content and proteins content were determined by standard method. Solubility index, absorption index and hygroscopicity were determined by method found in literature. Particle size distribution were obtained by laser diffraction granulometry. Location of the powder color in the Cielab color space and water activity were characterized by a colorimeter and an aw-value meter, respectively. Flow properties were characterized with FT4 powder rheometer; in particular compressibility and shearing test were performed. Air pressure and outlet temperature are key factors that directly impact the drying kinetics and powder characteristics during spray-drying process. It was shown that the air pressure affects the particle size distribution by impacting the size of droplet exiting the nozzle. Moreover, small particles lead to more cohesive powder and less saturated color of powders. Higher outlet temperature results in lower moisture level particles which are less sticky and can explain a spray-drying yield increase and the higher cohesiveness; it also leads to particle with low water activity because of the intense evaporation rate. However, it induces a high hygroscopicity, thus, powders tend to get wet rapidly if they are not well stored. On the other hand, high temperature provokes a decrease of native serum proteins which is positively correlated to gelation properties (gel point and firmness). Partial denaturation of serum proteins can improve functional properties of powder. The control of air pressure and outlet temperature during the spray-drying process significantly affects the physicochemical and functional properties of powder. This study permitted to better understand the links between physicochemical and functional properties of powder, to identify correlations between air pressure and outlet temperature. Therefore, mathematical models have been developed and the use of genetic algorithm will allow the optimization of powder functionalities.Keywords: dairy powders, spray-drying, powders functionalities, design of experiment
Procedia PDF Downloads 909 Date Palm Wastes Turning into Biochars for Phosphorus Recovery from Aqueous Solutions: Static and Dynamic Investigations
Authors: Salah Jellali, Nusiba Suliman, Yassine Charabi, Jamal Al-Sabahi, Ahmed Al Raeesi, Malik Al-Wardy, Mejdi Jeguirim
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Huge amounts of agricultural biomasses are worldwide produced. At the same time, large quantities of phosphorus are annually discharged into water bodies with possible serious effects onto the environment quality. The main objective of this work is to turn a local Omani biomass (date palm fronds wastes: DPFW) into an effective material for phosphorus recovery from aqueous and the reuse of this P-loaded material in agriculture as ecofriendly amendment. For this aim, the raw DPFW were firstly impregnated with 1 M salt separated solutions of CaCl₂, MgCl₂, FeCl₃, AlCl₃, and a mixture of MgCl₂/AlCl₃ for 24 h, and then pyrolyzed under N2 flow at 500 °C for 2 hours by using an adapted tubular furnace (Carbolite, UK). The synthetized biochars were deeply characterized through specific analyses concerning their morphology, structure, texture, and surface chemistry. These analyses included the use of a scanning electron microscope (SEM) coupled with an energy-dispersive X-Ray spectrometer (EDS), X-Ray diffraction (XRD), Fourier Transform Infrared (FTIR), sorption micrometrics, and X-ray Fluorescence (XRF) apparatus. Then, their efficiency in recovering phosphorus was investigated in batch mode for various contact times (1 min to 3 h), aqueous pH values (from 3 to 11), initial phosphorus concentrations (10-100 mg/L), presence of anions (nitrates, sulfates, and chlorides). In a second step, dynamic assays, by using laboratory columns (height of 30 cm and diameter of 3 cm), were performed in order to investigate the recovery of phosphorus by the modified biochar with a mixture of Mg/Al. The effect of the initial P concentration (25-100 mg/L), the bed depth height (3 to 8 g), and the flow rate (10-30 mL/min) was assessed. Experimental results showed that the biochars physico-chemical properties were very dependent on the type of the used modifying salt. The main affected parameters concerned the specific surface area, microporosity area, and the surface chemistry (pH of zero-point charge and available functional groups). These characteristics have significantly affected the phosphorus recovery efficiency from aqueous solutions. Indeed, the P removal efficiency in batch mode varies from about 5 mg/g for the Fe-modified biochar to more than 13 mg/g for the biochar functionalized with Mg/Al layered double hydroxides. Moreover, the P recovery seems to be a time dependent process and significantly affected by the pH of the aqueous media and the presence of foreign anions due to competition phenomenon. The laboratory column study of phosphorus recovery by the biochar functionalized with Mg/Al layered double hydroxides showed that this process is affected by the used phosphorus concentration, the flow rate, and especially the column bed depth height. Indeed, the phosphorus recovered amount increased from about 4.9 to more than 9.3 mg/g used biochar mass of 3 and 8 g, respectively. This work proved that salt-modified palm fronds-derived biochars could be considered as attractive and promising materials for phosphorus recovery from aqueous solutions even under dynamic conditions. The valorization of these P-loaded-modified biochars as eco-friendly amendment for agricultural soils is necessary will promote sustainability and circular economy concepts in the management of both liquid and solid wastes.Keywords: date palm wastes, Mg/Al double-layered hydroxides functionalized biochars, phosphorus, recovery, sustainability, circular economy
Procedia PDF Downloads 808 Study of Operating Conditions Impact on Physicochemical and Functional Properties of Dairy Powder Produced by Spray-drying
Authors: Adeline Meriaux, Claire Gaiani, Jennifer Burgain, Frantz Fournier, Lionel Muniglia, Jérémy Petit
Abstract:
Spray-drying process is widely used for the production of dairy powders for food and pharmaceuticals industries. It involves the atomization of a liquid feed into fine droplets, which are subsequently dried through contact with a hot air flow. The resulting powders permit transportation cost reduction and shelf life increase but can also exhibit various interesting functionalities (flowability, solubility, protein modification or acid gelation), depending on operating conditions and milk composition. Indeed, particles porosity, surface composition, lactose crystallization, protein denaturation, protein association or crust formation may change. Links between spray-drying conditions and physicochemical and functional properties of powders were investigated by a design of experiment methodology and analyzed by principal component analysis. Quadratic models were developed, and multicriteria optimization was carried out by the use of genetic algorithm. At the time of abstract submission, verification spray-drying trials are ongoing. To perform experiments, milk from dairy farm was collected, skimmed, froze and spray-dried at different air pressure (between 1 and 3 bars) and outlet temperature (between 75 and 95 °C). Dry matter, minerals content and proteins content were determined by standard method. Solubility index, absorption index and hygroscopicity were determined by method found in literature. Particle size distribution were obtained by laser diffraction granulometry. Location of the powder color in the Cielab color space and water activity were characterized by a colorimeter and an aw-value meter, respectively. Flow properties were characterized with FT4 powder rheometer; in particular, compressibility and shearing test were performed. Air pressure and outlet temperature are key factors that directly impact the drying kinetics and powder characteristics during spray-drying process. It was shown that the air pressure affects the particle size distribution by impacting the size of droplet exiting the nozzle. Moreover, small particles lead to more cohesive powder and less saturated color of powders. Higher outlet temperature results in lower moisture level particles which are less sticky and can explain a spray-drying yield increase and the higher cohesiveness; it also leads to particle with low water activity because of the intense evaporation rate. However, it induces a high hygroscopicity, thus, powders tend to get wet rapidly if they are not well stored. On the other hand, high temperature provokes a decrease of native serum proteins, which is positively correlated to gelation properties (gel point and firmness). Partial denaturation of serum proteins can improve functional properties of powder. The control of air pressure and outlet temperature during the spray-drying process significantly affects the physicochemical and functional properties of powder. This study permitted to better understand the links between physicochemical and functional properties of powder to identify correlations between air pressure and outlet temperature. Therefore, mathematical models have been developed, and the use of genetic algorithm will allow the optimization of powder functionalities.Keywords: dairy powders, spray-drying, powders functionalities, design of experiment
Procedia PDF Downloads 637 Microstructural Characterization of Bitumen/Montmorillonite/Isocyanate Composites by Atomic Force Microscopy
Authors: Francisco J. Ortega, Claudia Roman, Moisés García-Morales, Francisco J. Navarro
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Asphaltic bitumen has been largely used in both industrial and civil engineering, mostly in pavement construction and roofing membrane manufacture. However, bitumen as such is greatly susceptible to temperature variations, and dramatically changes its in-service behavior from a viscoelastic liquid, at medium-high temperatures, to a brittle solid at low temperatures. Bitumen modification prevents these problems and imparts improved performance. Isocyanates like polymeric MDI (mixture of 4,4′-diphenylmethane di-isocyanate, 2,4’ and 2,2’ isomers, and higher homologues) have shown to remarkably enhance bitumen properties at the highest in-service temperatures expected. This comes from the reaction between the –NCO pendant groups of the oligomer and the most polar groups of asphaltenes and resins in bitumen. In addition, oxygen diffusion and/or UV radiation may provoke bitumen hardening and ageing. With the purpose of minimizing these effects, nano-layered-silicates (nanoclays) are increasingly being added to bitumen formulations. Montmorillonites, a type of naturally occurring mineral, may produce a nanometer scale dispersion which improves bitumen thermal, mechanical and barrier properties. In order to increase their lipophilicity, these nanoclays are normally treated so that organic cations substitute the inorganic cations located in their intergallery spacing. In the present work, the combined effect of polymeric MDI and the commercial montmorillonite Cloisite® 20A was evaluated. A selected bitumen with penetration within the range 160/220 was modified with 10 wt.% Cloisite® 20A and 2 wt.% polymeric MDI, and the resulting ternary composites were characterized by linear rheology, X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). The rheological tests evidenced a notable solid-like behavior at the highest temperatures studied when bitumen was just loaded with 10 wt.% Cloisite® 20A and high-shear blended for 20 minutes. However, if polymeric MDI was involved, the sequence of addition exerted a decisive control on the linear rheology of the final ternary composites. Hence, in bitumen/Cloisite® 20A/polymeric MDI formulations, the previous solid-like behavior disappeared. By contrast, an inversion in the order of addition (bitumen/polymeric MDI/ Cloisite® 20A) enhanced further the solid-like behavior imparted by the nanoclay. In order to gain a better understanding of the factors that govern the linear rheology of these ternary composites, a morphological and microstructural characterization based on XRD and AFM was conducted. XRD demonstrated the existence of clay stacks intercalated by bitumen molecules to some degree. However, the XRD technique cannot provide detailed information on the extent of nanoclay delamination, unless the entire fraction has effectively been fully delaminated (situation in which no peak is observed). Furthermore, XRD was unable to provide precise knowledge neither about the spatial distribution of the intercalated/exfoliated platelets nor about the presence of other structures at larger length scales. In contrast, AFM proved its power at providing conclusive information on the morphology of the composites at the nanometer scale and at revealing the structural modification that yielded the rheological properties observed. It was concluded that high-shear blending brought about a nanoclay-reinforced network. As for the bitumen/Cloisite® 20A/polymeric MDI formulations, the solid-like behavior was destroyed as a result of the agglomeration of the nanoclay platelets promoted by chemical reactions.Keywords: Atomic Force Microscopy, bitumen, composite, isocyanate, montmorillonite.
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