Search results for: mesoporous Al₂O₃

Authors: Abdul Salam Turkmani

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Clay of the northern Palmyra region is one of the most important raw materials used in the Syrian ceramics industry. This study is focused on the evaluation of various laboratory analyses such as chemical analysis (XRF), mineral X-ray diffraction analysis (XRD), differential thermal analysis (DTA), and semi-industrial tests carried out on samples collected on two representative locations of the upper Oligocene in AlMkamen valley (MK) and lower Miocene in AlZukara valley (ZR) of the northern part of Palmyra, Syria. Chemical results classify the (MK) and (ZR) clays as semi-plastic red clay slightly carbonate and (eliminate probable) illite-chlorite clays with a very fine particle size distribution. Content of SiO₂ between 46.28-57.66%, Al2O3 13.81-25.2%, Fe₂O₃ 3.47-11.58%, CaO 1.15-7.19%, Na₂O+K₂O varied between 3.34-3.71%. Based on clay chemical composition and iron and carbonate content, these deposits can be considered as red firing clays. Their mineralogical composition is mainly represented by illite, kaolinite and quartz, and accessories minerals such as calcite, feldspar, phillipsite, and goethite. The results of the DTA test confirm the presence of gypsum and quartz phases in (MK) clay. Ceramic testing shows good green and dry bending strength values, which varied between 9-14 kg/cm², at 1160°C to 1180°C. Water absorption moves from 14.6 % at 1120°C to 2.2% at 1180°C to 1.6% at 1200°C. Breaking load after firing changes from 400 to 590 kg/cm². At 1200°C (MK), clay reaches perfect vitrification. After firing, the color of the clay changes from orange-hazel to red-brown at 1180°C. Technological results confirmed the suitability of the studied clays to produce floor and wall ceramic tiles. Using one of the two types of clay into the ceramic body or both types together gave satisfactory industrial results.

Keywords: ceramic, clay, industry , Palmyra

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Authors: Vidula Shevade, B. J. Nagare, Sajeev Chacko

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First principles simulation, meaning density functional theory (DFT) calculations with plane waves and pseudopotential, has become a prized technique in condensed matter theory. Nanoparticles (NP) have been known to possess good catalytic activities, especially for molecules such as CO, O₂, etc. Among the metal NPs, Aluminium based NPs are also widely known for their catalytic properties. Aluminium metal is a lightweight, excellent electrical, and thermal abundant chemical element in the earth’s crust. Aluminium NPs, when added to solid rocket fuel, help improve the combustion speed and considerably increase combustion heat and combustion stability. Adding aluminium NPs into normal Al/Al₂O₃ powder improves the sintering processes of the ceramics, with high heat transfer performance, increased density, and enhanced thermal conductivity of the sinter. We used VASP and Gaussian 0₃ package to compute the geometries, electronic structure, and bonding properties of Al₁₂Ni as well as its interaction with O₂ and CO molecules. Several MD simulations were carried out using VASP at various temperatures from which hundreds of structures were optimized, leading to 24 unique structures. These structures were then further optimized through a Gaussian package. The lowest energy structure of Al₁₂Ni has been reported to be a singlet. However, through our extensive search, we found a triplet state to be lower in energy. In our structure, the Ni atom is found to be on the surface, which gives the non-zero magnetic moment. Incidentally, O2 and CO molecules are also triplet in nature, due to which the Al₁₂-Ni cluster is likely to facilitate the oxidation process of the CO molecule. Our results show that the most favourable site for the CO molecule is the Ni atom and that for the O₂ molecule is the Al atom that is nearest to the Ni atom. Al₁₂Ni-O₂ and Al₁₂-Ni-CO structures we extracted using VMD. Al₁₂Ni nanocluster, due to in triplet electronic structure configuration, indicates it to be a potential candidate as a catalyst for oxidation of CO molecules.

Keywords: catalyst, gaussian, nanoparticles, oxidation

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Authors: B. Chen, F. Kuznik, M. Horgnies, K. Johannes, V. Morin, E. Gengembre

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More attention on renewable energy has been done after the achievement of Paris Agreement against climate change. Solar-based technology is supposed to be one of the most promising green energy technologies for residential buildings since its widely thermal usage for hot water and heating. However, the seasonal mismatch between its production and consumption makes buildings need an energy storage system to improve the efficiency of renewable energy use. Indeed, there exist already different kinds of energy storage systems using sensible or latent heat. With the consideration of energy dissipation during storage and low energy density for above two methods, thermochemical energy storage is then recommended. Recently, ettringite (3CaO∙Al₂O₃∙3CaSO₄∙32H₂O) based materials have been reported as potential thermochemical storage materials because of high energy density (~500 kWh/m³), low material cost (700 €/m³) and low storage temperature (~60-70°C), compared to reported salt hydrates like SrBr₂·6H₂O (42 k€/m³, ~80°C), LaCl₃·7H₂O (38 k€/m³, ~100°C) and MgSO₄·7H₂O (5 k€/m³, ~150°C). Therefore, they have the possibility to be largely used in building sector with being coupled to normal solar panel systems. On the other side, the lack in terms of extensive examination leads to poor knowledge on their thermal properties and limit maturity of this technology. The aim of this work is to develop a modular reactor adapting to thermal characterizations of ettringite-based material particles of different sizes. The filled materials in the reactor can be self-compacted vertically to ensure hot air or humid air goes through homogenously. Additionally, quick assembly and modification of reactor, like LEGO™ plastic blocks, make it suitable to distinct thermochemical energy storage material samples with different weights (from some grams to several kilograms). In our case, quantity of stored and released energy, best work conditions and even chemical durability of ettringite-based materials have been investigated.

Keywords: dehydration, ettringite, hydration, modular reactor, thermochemical energy storage

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Authors: Biswajit Pal, Amit Mallik, Anil K. Barik

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Current years have witnessed a phenomenal growth in the research on the rare earth-doped transparent host materials, the essential components in optoelectronics that meet up the increasing demand for fabrication of high quality optical devices especially in telecommunication system. The combination of low phonon energy (because of fluoride environment) and high chemical durability with superior mechanical stability (due to oxide environment) makes the oxyfluoride glass–ceramics the promising and useful materials in optoelectronics. The present work reports on the undoped and doped (1 mol% Pr2O3) glass ceramics of composition 16.52 Al2O3•1.5AlF3• 12.65LaF3•4.33Na2O•64.85 SiO2 (mol%), prepared by melting technique initially that follows annealation at 450 ºC for 1 h. The glass samples so obtained were heat treated at constant 600 ºC with a variation in heat treatment schedule (10- 80 h). TEM techniques were employed to structurally characterize the glass samples. Pr2O3 affects the phase separation in the glass and delays the onset of crystallization in the glass ceramic. The modified crystallization mechanism is established from the analysis of advanced STEM/EDXS results. The phase separated droplets after annealing turn into 10-20 nm of LaF3 nano crystals those upon scrutiny are found to be dotted with the doped Pr3+ ions within the crystals themselves. The EDXS results also suggest that the inner LaF3 crystal core is swallowed by an Al enriched layer that follows a Si enriched surrounding shell as the outer core. This greatly increases the viscosity in the periphery of the crystals that restricts further crystal growth to account for the formation of nano sized crystals.

Keywords: advanced STEM/EDXS, crystallization mechanism, nano crystals, pr3+ ion doped glass and glass ceramic, structural characterization

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Authors: Ala’a H. Al-Muhtaseb, Farrukh Jamil, Sandeep K. Saxena

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The fast growth rate of energy consumption along with world population expected to demand 50% more energy by 2030 than nowadays. At present, the energy demand is mostly provided by limited fossil fuel sources such as oil, natural gas, and coal that are resulting in dramatic increase in CO2 emissions from combustion of fossil fuels. The growth of the biodiesel industry over the last decade has resulted in a price drop because glycerol is obtained as a by-product during transesterification of vegetable oil or animal fats, which accounts for one tenth of every gallon of biodiesel produced. The production of oxygenates from glycerol gains much importance due to the excellent diesel-blending property of the oxygenates that not only improve the quality of the fuel but also increases the overall yield of the biodiesel in helping to meet the target for energy production from renewable sources for transport in the energy utilization directives. The reaction of bio-glycerol with bio-acetone was carried out in a magnetically stirred two necked round bottom flaskS. Condensation of bio-glycerol with acetone in the presence of various modified forms of beta zeolite has been done for synthesizing solketal (AB-2 modified with nitric acid, AB-3 modified with oxalic acid). Among all modified forms of beta zeolite, AB-2 showed the best performance for maximum glycerol conversion 94.26 % with 94.21 % solketal selectivity and minimum acetal formation 0.05 %. The physiochemical properties of parent beta zeolite and all its modified forms were analyzed by XRD, SEM, TEM, BET, FTIR and TPD. It has been revealed that AB-2 catalysts with high pore volume and surface area gave high glycerol conversion with maximum solketal selectivity. Despite this, the crystallinity of AB-3 was lower than AB-2 which helps to provide the shorter path length for reactants and product but due high pore volume AB-2 was preferred which gave maximum bio-glycerol conversion. Temperature does matter the glycerol conversion and selectivity of solketal, as it increases from 40 ºC to 60 ºC the conversion of glycerol rises from 80.04 % to 94.26 % and selectivity of solketal from 80.0 % to 94.21 % but further increase in temperature to 100 ºC glycerol conversion reduced to 93.06 % and solketal selectivity to 92.08 %. AB-2 was found to be highly stable as up to 4 repeated experimental runs there was less than 10% decrease in its activity. This process offers an attractive route for converting bio-glycerol, the main by-product of biodiesel to solketal with bio-acetone; a value-added green product with potential industrial applications as a valuable green fuel additive or combustion promoter for gasoline/diesel engines.

Keywords: beta-zeolite, bio-glycerol, catalyst, solketal

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Authors: Barbara Bialecka, Zdzislaw Adamczyk, Magdalena Cempa

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In the work, the results of investigations into the hydrothermal zeolitization of fly ash from hard coal combustion in one of Polish Power Station have been presented. The chemical composition of the ash was determined by the method of X-ray fluorescence (XRF), whereas the phases of both fly ash and the products after synthesis were identified using microscopic observations, X-ray diffraction analysis (XRD) as well as electron scanning microscopy with measurements of the chemical compositions in micro areas (SEM/EDS). The synthesis was carried out with various concentrations of NaOH solution (3M, 4M and 6M) in the following conditions: synthesis temperature – 80ᵒC, synthesis time – 16 hours, volume of NaOH solution – 350ml, fly ash mass – 14g. The main chemical components of fly ash were SiO₂ and Al₂O₃, the contents of which reached 51.62 and 28.14%mas., respectively. The input ash contained mainly such phases as mullite, quarz, magnetite, and glass. The research results indicate that the phase composition of products after zeolitization was differentiated. The material after synthesis in 3M NaOH solution was found to contain mullite, quarz, magnetite, and Na-LSX zeolite. The products of synthesis in 4M NaOH solution were very similar to those in 3M solution (mullite, quarz, magnetite, Na-LSX zeolite), but they additionally contained hydrosodalite. The material after synthesis in 6M NaOH solution contains mullite, quarz, magnetite (similarly to synthesis in 3M and 4M NaOH solition) and additionally hydrosodalite. Therefore, the products of synthesis contain relic components from the fly ash input sample in the form of mullite, quarz, and magnetite, as well as new phases, which are Na-LSX zeolite and hydrosodalite. It should be noted that the products of synthesis in the case of 4M NaOH solution contained both new phases (Na-LSX zeolite and hydrosodalite), while the products from the extreme concentration of NaOH solutions (3M and 6M) contained only one of them. Observations in the scanning electron microscope revealed the new phases’ morphology. It was found that Na-LSX zeolite formed cubic crystals, whereas hydrosodalite formed characteristic aggregations. The results of investigations into the chemical composition in the micro area of phase grains in the products after synthesis reveal some dependencies, among others a characteristic increase in the content of sodium, related to the increased concentration of NaOH solution.

Keywords: Na-LSX, fly ash, hydrosodalite, zeolite

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Authors: Suresh Kumar Verma, Jugal Kishore Das, Ealisha Jha, Mrutyunjay Suar, SKS Parashar

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In recent years nanoforms of inorganic metallic oxides has attracted a lot of interest due to their small size and significantly improved physical, chemical and biological properties compared to their molecular precursor. Some of the inorganic materials such as TiO2, ZnO, MgO, CaO, Al2O3 have been extensively used in biological applications. Zinc Oxide is a Wurtzite-type semiconductor and piezo-electric material exhibiting excellent electrical, optical and chemical properties with a band energy gap of 3.1-3.4 eV. Nanoforms of Zinc Oxide (ZnO) are increasingly recognised for their utility in biological application. The significant physical parameters such as surface area, particle size, surface charge and Zeta potential of Zinc Oxide (ZnO) nanoparticles makes it suitable for the uptake, persistance, biological, and chemical activities inside the living cells. The present study shows the effect of intrinsic defects of ZnO nanocrystals synthesized by high energy ball milling (HEBM) technique in their antibacterial activities. Bulk Zinc oxide purchased from market were ball milled for 7 h, 10 h, and 15 h respectively to produce nanosized Zinc Oxide. The structural and optical modification of such synthesized particles were determined by X-ray diffraction (XRD), Scanning Electron Microscopy and Electron Paramagnetic Resonance (EPR). The antibacterial property of synthesized Zinc Oxide nanoparticles was tested using well diffusion, minimum inhibitory Concentration, minimum bacteriocidal concentration, reactive oxygen species (ROS) estimation and membrane potential determination methods. In this study we observed that antibacterial activity of ZnO nanoparticles is because of the intrinsic defects that exist as a function of difference in size and milling time.

Keywords: high energy ball milling, ZnO nanoparticles, EPR, Antibacterial properties

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Authors: Ben Yahia Nouha, Sebei Abdelaziz, Boussen Slim, Chaabani Fredj

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The present work aims to determine mineralogical and geochemical characteristics of siliceous rock levels and to clarify the origin through geochemical arguments. This study was performed on the deposit of Tabarka-Babouch, which belongs to the northwestern of Tunisia; they spread out the later Miocene. Investigations were carried out to study mineralogical structure by XRD and chemical analysis by ICP-AES. The X-ray diffraction (XRD) patterns of the powdered natural rocks show that the Babouchite is composed mainly of quartz and clay minerals (smectite, illite, and kaolinite). Siliceous rocks contain quartz as a major silica mineral, which is characterized by two broad reflections at the vicinity of 4.26Å and 3.34 Å, respectively, with a total lack of opal-CT. That confirms that these siliceous rocks are quartz-rich (can reach 90%). Indeed, the amounts of all clay minerals (ACM), constituted essentially by smectite marked by a close association with illite and kaolinite, are relatively high, where their percentages vary from 7 to 46%. Chemical analyses show that the major oxide contents are consistent with mineralogical observations. It reveals that the siliceous rocks of the Babouchite formation are rich in SiO₂. The data of whole-rock chemical analyses indicate that the SiO₂ content is generally in the range 73-91 wt.%; (average: 80.43 wt.%). The concentration of Al₂O₃, which represent the detrital fractions in the studied samples, varies from 3.99 to 10.55 wt. % and Fe₂O₃ from 0.73 to 4.41wt. %. The low levels recorded in CaO (%) show that the carbonate is considered impurities. However, these rocks contain a low amount of some others oxides, such as the following: Na₂O, MgO, K₂O, and TiO₂. The trace elemental distributions also vary with high Sr (up to 84.55 ppm), Cu (5–127 ppm), and Zn (up to 124 ppm), with a relatively lower concentration of Co (2.43-25.54 ppm), Cr (10–61 ppm) and Pb (8-22ppm). The Babouchite siliceous rocks of northwestern of Tunisia have generally high Al/ (Al+Fe+Mn) values (0.63-0.83). The majority of Al/ (Al+Fe+Mn) values are nearly of 0.6, which is the biogenic end-member. Thus, Al/ (Al+Fe+Mn) values revealed the biogenic origin of silica.

Keywords: siliceous rocks, Babouchite formation, XRD, chemical analysis, biogenic silica, Northwestern of Tunisia

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Authors: Suresh Vanguri, Suresh Palla, Prasad G., Ramaswamy V., Kalyani K. V., Chaturvedi S. K., Mohapatra B. N., Sunder Rao TBVN

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The utilization of industrial waste materials and by-products in the cement industry helps in the conservation of natural resources besides avoiding the problems arising due to waste dumping. The use of non-carbonated materials as raw mix components in clinker manufacturing is identified as one of the key areas to reduce Green House Gas (GHG) emissions. Chrome sludge is a waste material generated from the manufacturing process of sodium dichromate. This paper aims to present studies on the use of chrome sludge in clinker manufacturing, its impact on the development of clinker mineral phases and on the cement properties. Chrome sludge was found to contain substantial amounts of CaO, Fe2O3 and Al2O3 and therefore was used to replace some conventional sources of alumina and iron in the raw mix. Different mixes were prepared by varying the chrome sludge content from 0 to 5 % and the mixes were evaluated for burnability. Laboratory prepared clinker samples were evaluated for qualitative and quantitative mineralogy using X-ray Diffraction Studies (XRD). Optical microscopy was employed to study the distribution of clinker phases, their granulometry and mineralogy. Since chrome sludge also contains considerable amounts of chromium, studies were conducted on the leachability of heavy elements in the chrome sludge as well as in the resultant cement samples. Estimation of heavy elements, including chromium was carried out using ICP-OES. Further, the state of chromium valence, Cr (III) & Cr (VI), was studied using conventional chemical analysis methods coupled with UV-VIS spectroscopy. Assimilation of chromium in the clinker phases was investigated using SEM-EDXA studies. Bulk cement was prepared from the clinker to study the effect of chromium sludge on the cement properties such as setting time, soundness, strength development against the control cement. Studies indicated that chrome sludge can be successfully utilized and its content needs to be optimized based on raw material characteristics.

Keywords: chrome sludge, leaching, mineralogy, non-carbonate materials

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Authors: Xiping Guo, Fanglin Ge, Ping Guan

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Refractory high entropy alloys are alternative materials expected to be employed at high temperatures. The comprehensive changes of microstructure and properties of NbTiZrCrAl refractory high entropy alloys are systematically studied by adjusting Al content. Five kinds of button alloy ingots with different contents of Al in NbTiZrCrAlX (X=0, 0.2, 0.5, 0.75, 1.0) were prepared by vacuum non-consumable arc melting technology. The microstructure analysis results show that the five alloys are composed of BCC solid solution phase rich in Nb and Ti and Laves phase rich in Cr, Zr, and Al. The addition of Al changes the structure from hypoeutectic to hypereutectic, increases the proportion of Laves phase, and changes the structure from cubic C15 to hexagonal C14. The hardness and fracture toughness of the five alloys were tested at room temperature, and the compressive mechanical properties were tested at 1000℃. The results showed that the addition of Al increased the proportion of Laves phase and decreased the proportion of the BCC phase, thus increasing the hardness and decreasing the fracture toughness at room temperature. However, at 1000℃, the strength of 0.5Al and 0.75Al alloys whose composition is close to the eutectic point is the best, which indicates that the eutectic structure is of great significance for the improvement of high temperature strength of NbTiZrCrAl refractory high entropy alloys. The five alloys were oxidized for 1 h and 20 h in static air at 1000℃. The results show that only the oxide film of 0Al alloy falls off after oxidizing for 1 h at 1000℃. After 20h, the oxide film of all the alloys fell off, but the oxide film of alloys containing Al was more dense and complete. By producing protective oxide Al₂O₃, inhibiting the preferential oxidation of Zr, promoting the preferential oxidation of Ti, and combination of Cr₂O₃ and Nb₂O₅ to form CrNbO₄, Al significantly improves the high temperature oxidation resistance of NbTiZrCrAl refractory high entropy alloys.

Keywords: NbTiZrCrAl, refractory high entropy alloy, al content, microstructural evolution, room temperature mechanical properties, high temperature compressive strength, oxidation resistance

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Authors: Eva Ujaczki, Rama Krishna Chinnam, Ronan Courtney, Syed A. M. Tofail, Lisa O'Donoghue

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Concrete is the second most widely used material in the world and is made of cement, sand, and aggregates. Cement is a hydraulic binder which reacts with water to form a solid material. In the cement manufacturing process, the right mix of minerals from mined natural rocks, e.g., limestone is melted in a kiln at 1450 °C to form a new compound, clinker. In the final stage, the clinker is milled into a fine cement powder. The principal cement types manufactured in Ireland are: 1) CEM I – Portland cement; 2) CEM II/A – Portland-fly ash cement; 3) CEM II/A – Portland-limestone cement and 4) CEM III/A – Portland-round granulated blast furnace slag (GGBS). The production of eco-efficient, blended cement (CEM II, CEM III) reduces CO₂ emission and improves energy efficiency compared to traditional cements. Blended cements are produced locally in Ireland and more than 80% of produced cement is blended. These eco-efficient, blended cements are a relatively new class of construction materials and a kind of geopolymer binders. From a terminological point of view, geopolymer cement is a binding system that is able to harden at room temperature. Geopolymers do not require calcium-silicate-hydrate gel but utilize the polycondensation of SiO₂ and Al₂O₃ precursors to achieve a superior strength level. Geopolymer materials are usually synthesized using an aluminosilicate raw material and an activating solution which is mainly composed of NaOH or KOH and Na₂SiO₃. Cement is the essential ingredient in concrete which is vital for economic growth of countries. The challenge for the global cement industry is to reach to increasing demand at the same time recognize the need for sustainable usage of resources. Therefore, in this research, we investigated the potential for Irish wastes to be used in geopolymer cement type applications through a national stakeholder workshop with the Irish construction sector and relevant stakeholders. This paper aims at summarizing Irish stakeholder’s perspective for introducing new secondary raw materials, e.g., bauxite residue or increasing the fly ash addition into cement for eco-efficient cement production.

Keywords: eco-efficient, cement, geopolymer, blending

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Authors: Qing Zhang, Janak L. Pathak, Macro N. Helder, Richard T. Jaspers, Yin Xiao

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Introduction: Nanomaterial-based bone regeneration is greatly influenced by the immune microenvironment. Tissue-engineered nanomaterials mediate the inflammatory response of macrophages to regulate bone regeneration. Silica nanoparticles have been widely used in tissue engineering-related preclinical studies. However, the effect of topological features on the surface of silica nanoparticles on the immune response of macrophages remains unknown. Purposes: The aims of this research are to compare the influences of normal and pollen-like silica nano-surface topography on macrophage immune responses and to obtain insight into their potential regulatory mechanisms. Method: Macrophages (RAW 264.7 cells) were exposed to mesoporous silica nanoparticles with normal morphology (MSNs) and pollen-like morphology (PMSNs). RNA-seq, RT-qPCR, and LSCM were used to assess the changes in expression levels of immune response-related genes and proteins. SEM and TEM were executed to evaluate the contact and adherence of silica nanoparticles by macrophages. For the assessment of the immunomodulation-mediated osteogenic potential, BMSCs were cultured with conditioned medium (CM) from LPS pre-stimulated macrophage cultures treated with MSNs or PMSNs. Osteoimmunomodulatory potential of MSNs and PMSNs in vivo was tested in a mouse cranial bone osteolysis model. Results: The results of the RNA-seq, RT-qPCR, and LSCM assays showed that PMSNs inhibited the expression of pro-inflammatory genes and proteins in macrophages. SEM images showed distinct macrophage membrane surface binding patterns of MSNs and PMSNs. MSNs were more evenly dispersed across the macrophage cell membrane, while PMSNs were aggregated. PMSNs-induced macrophage anti-inflammatory response was associated with upregulation of the cell surface receptor CD28 and inhibition of ERK phosphorylation. TEM images showed that both MSNs and PMSNs could be phagocytosed by macrophages, and inhibiting nanoparticle phagocytosis did not affect the expression of anti-inflammatory genes and proteins. Moreover, PMSNs-induced conditioned medium from macrophages enhanced BMP-2 expression and osteogenic differentiation mBMSCs. Similarly, PMSNs prevented LPS-induced bone resorption via downregulation of inflammatory reaction. Conclusions: PMSNs can promote bone regeneration by modulating osteoimmunological processes through surface topography. The study offers insights into how surface physical contact cues can modulate the regulation of osteoimmunology and provides a basis for the application of nanoparticles with pollen-like morphology to affect immunomodulation in bone tissue engineering and regeneration.

Keywords: physical contact, osteoimmunology, macrophages, silica nanoparticles, surface morphology, membrane receptor, osteogenesis, inflammation

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Authors: Laura Vitola, Diana Bajare, Genadijs Sahmenko, Girts Bumanis

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About 8 % of CO2 emission in the world is produced by concrete industry therefore replacement of cement in concrete composition by additives with pozzolanic activity would give a significant impact on the environment. Material which contains silica SiO2 or amorphous silica SiO2 together with aluminum dioxide Al2O3 is called pozzolana type additives in the concrete industry. Pozzolana additives are possible to obtain from recycling industry and different production by-products such as processed bulb boric silicate (DRL type) and lead (LB type) glass, coal combustion bottom ash, utilized brick pieces and biomass ash, thus solving utilization problem which is so important in the world, as well as practically using materials which previously were considered as unusable. In the literature, there is no summarized method which could be used for quick waste-product pozzolana activity evaluation without the performance of wide researches related to the production of innumerable concrete contents and samples in the literature. Besides it is important to understand which parameters should be predicted to characterize the efficiency of waste-products. Simple methods of pozzolana activity increase for different types of waste-products are also determined. The aim of this study is to evaluate effectiveness of the different types of waste materials and industrial by-products (coal combustion bottom ash, biomass ash, waste glass, waste kaolin and calcined illite clays), and determine which parameters have the greatest impact on pozzolanic activity. By using materials, which previously were considered as unusable and landfilled, in concrete industry basic utilization problems will be partially solved. The optimal methods for treatment of waste materials and industrial by–products were detected with the purpose to increase their pozzolanic activity and produce substitutes for cement in the concrete industry. Usage of mentioned pozzolanic allows us to replace of necessary cement amount till 20% without reducing the compressive strength of concrete.

Keywords: cement substitutes, micro and nano fillers, pozzolanic properties, specific surface area, particle size, waste products

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Authors: Lucie Speyer, Vincent Lecocq, Séverine Humbert, Antoine Hugon

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Mesoporous alumina is commonly used as a catalyst support for the hydrotreating of heavy petroleum cuts. The process of fabrication usually involves: the synthesis of the boehmite AlOOH precursor, a kneading-extrusion step, and a calcination in order to obtain the final alumina extrudates. Alumina is described as a complex porous medium, generally agglomerates constituted of aggregated nanocrystallites. Its porous texture directly influences the active phase deposition and mass transfer, and the catalytic properties. Then, it is easy to figure out that each step of the fabrication of the supports has a role on the building of their porous network, and has to be well understood to optimize the process. The synthesis of boehmite by precipitation of aluminum salts was extensively studied in the literature and the effect of various parameters, such as temperature or pH, are known to influence the size and shape of the crystallites and the specific surface area of the support. The calcination step, through the topotactic transition from boehmite to alumina, determines the final properties of the support and can tune the surface area, pore volume and pore diameters from those of boehmite. However, the kneading extrusion step has been subject to a very few studies. It generally consists in two steps: an acid, then a basic kneading, where the boehmite powder is introduced in a mixer and successively added with an acid and a base solution to form an extrudable paste. During the acid kneading, the induced positive charges on the hydroxyl surface groups of boehmite create an electrostatic repulsion which tends to separate the aggregates and even, following the conditions, the crystallites. The basic kneading, by reducing the surface charges, leads to a flocculation phenomenon and can control the reforming of the overall structure. The separation and reassembling of the particles constituting the boehmite paste have a quite obvious influence on the textural properties of the material. In this work, we are focused on the influence of the kneading step on the alumina catalysts supports. Starting from an industrial boehmite, extrudates are prepared using various kneading conditions. The samples are studied by nitrogen physisorption in order to analyze the evolution of the textural properties, and by synchrotron small-angle X-ray scattering (SAXS), a more original method which brings information about agglomeration and aggregation of the samples. The coupling of physisorption and SAXS enables a precise description of the samples, as same as an accurate monitoring of their evolution as a function of the kneading conditions. These ones are found to have a strong influence of the pore volume and pore size distribution of the supports. A mechanism of evolution of the texture during the kneading step is proposed and could be attractive in order to optimize the texture of the supports and then, their catalytic performances.

Keywords: alumina catalyst support, kneading, nitrogen physisorption, small-angle X-ray scattering

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Authors: Dileep Maarisetty, Janaki Komandur, Saroj S. Baral

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In the current work, photocatalytic degradation of phenol was carried both in UV and visible light to find the slowest step that is limiting the rate of photo-degradation process. Characterization such as XRD, SEM, FT-IR, TEM, XPS, UV-DRS, PL, BET, UPS, ESR and zeta potential experiments were conducted to assess the credibility of catalysts in boosting the photocatalytic activity. To explore the synergy, TiO₂ was doped with graphene and alumina. The orbital hybridization with alumina doping (mediated by graphene) resulted in higher electron transfer from the conduction band of TiO₂ to alumina surface where oxygen reduction reactions (ORR) occur. Besides, the doping of alumina and graphene introduced defects into Ti lattice and helped in improving the adsorptive properties of modified photo-catalyst. Results showed that these defects promoted the oxygen reduction reactions (ORR) on the catalyst’s surface. ORR activity aims at producing reactive oxygen species (ROS). These ROS species oxidizes the phenol molecules which is adsorbed on the surface of photo-catalysts, thereby driving the photocatalytic reactions. Since mass transfer is considered as rate limiting step, various mathematical models were applied to the experimental data to probe the best fit. By varying the parameters, it was found that intra-particle diffusion was the slowest step in the degradation process. Lagergren model gave the best R² values indicating the nature of rate kinetics. Similarly, different adsorption isotherms were employed and realized that Langmuir isotherm suits the best with tremendous increase in uptake capacity (mg/g) of TiO₂-rGO-Al₂O₃ as compared undoped TiO₂. This further assisted in higher adsorption of phenol molecules. The results obtained from experimental, kinetic modelling and adsorption isotherms; it is concluded that apart from changes in surface, optoelectronic and morphological properties that enhanced the photocatalytic activity, the intra-particle diffusion within the catalyst’s pores serve as rate-limiting step in deciding the fate of photo-catalytic degradation of phenol.

Keywords: ORR, phenol degradation, photo-catalyst, rate kinetics

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Authors: O. Fiquet, P. Lemarignier

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Additive manufacturing may find numerous applications in the nuclear industry, for the same reason as for other industries, to enlarge design possibilities and performances and develop fabrication methods as a flexible route for future innovation. Additive Manufacturing applications in the design of structural metallic components for reactors are already developed at a high Technology Readiness Level (TRL). In the case of a Pressured Water Reactor using uranium oxide fuel pellets, which are ceramics, the transposition of already optimized Additive Manufacturing (AM) processes to UO₂ remains a challenge, and the progress remains slow because, to our best knowledge, only a few laboratories have the capability of developing processes applicable to UO₂. After the Fukushima accident, numerous research fields emerged with the study of ATF (Accident tolerant Fuel) fuel concepts, which aimed to improve fuel behaviour. One item concerns the increase of the pellet thermal performance by, for example, the addition of high thermal conductivity material into fissile UO₂. This additive phase may be metallic, and the end product will constitute a CERMET composite. Innovative designs of an internal metallic framework are proposed based on predictive calculations. However, because the well-known reference pellet manufacturing methods impose many limitations, manufacturing such a composite remains an arduous task. Therefore, the AM process appears as a means of broadening the design possibilities of CERMET manufacturing. If the external form remains a standard cylindrical fuel pellet, the internal metallic design remains to be optimized based on process capabilities. This project also considers the limitation to a maximum of 10% volume of metal, which is a constraint neutron physics considerations impose. The AM technique chosen for this development is robocasting because of its simplicity and low-cost equipment. It remains, however, a challenge to adapt a ceramic 3D printing process for the fabrication of UO₂ fuel. The investigation starts with surrogate material, and the optimization of slurry feedstock is based on alumina. The paper will present the first printing of Al2O3-Mo CERMET and the expected transition from ceramic-based alumina to UO₂ CERMET.

Keywords: nuclear, fuel, CERMET, robocasting

Procedia PDF Downloads 31

Authors: Longlong Zhang, Xiaohua Zhu, Ping Zhao, Yu Wang

Abstract:

The construction of mines, railways, highways, water conservancy projects, etc., have formed a large number of high steep slope wounds in China. Under the premise of slope stability and safety, the minimum cost, green and close to natural wound space repair, has become a new problem. Nowadays, in situ element testing and analysis, monitoring, field quantitative factor classification, and assignment evaluation will produce vast amounts of data. Data processing and analysis will inevitably differentiate the morphology, mineral composition, physicochemical properties between rock wounds, by which to dynamically match the appropriate techniques and materials for restoration. In the present research, based on the grid partition of the slope surface, tested the content of the combined oxide of rock mineral (SiO₂, CaO, MgO, Al₂O₃, Fe₃O₄, etc.), and classified and assigned values to the hardness and breakage of rock texture. The data of essential factors are interpolated and normalized in GIS, which formed the differential zoning map of slope space. According to the physical and chemical properties and spatial morphology of rocks in different zones, organic acids (plant waste fruit, fruit residue, etc.), natural mineral powder (zeolite, apatite, kaolin, etc.), water-retaining agent, and plant gum (melon powder) were mixed in different proportions to form rock aging agents. To spray the aging agent with different formulas on the slopes in different sections can affectively age the fresh rock wound, providing convenience for seed implantation, and reducing the transformation of heavy metals in the rocks. Through many practical engineering practices, a dynamic data platform of rock aging agent formula system is formed, which provides materials for the restoration of different slopes. It will also provide a guideline for the mixed-use of various natural materials to solve the complex, non-uniformity ecological restoration problem.

Keywords: data-driven, dynamic state, high steep slope, rock aging agent, wounds

Procedia PDF Downloads 85

Authors: Mahamuda Sk, Srinivasa Rao Allam, Vijaya Prakash G.

Abstract:

The different concentrations of Eu3+ ions doped in Oxy-fluoroborate glasses of composition 60 B2O3-10 BaF2-10 CaF2-15 CaF2- (5-x) Al2O3 -x Eu2O3 where x = 0.1, 0.5, 1.0 and 2.0 mol%, have been prepared by conventional melt quenching technique and are characterized through absorption and photoluminescence (PL), decay, color chromaticity and Confocal measurements. The absorption spectra of all the glasses consists of six peaks corresponding to the transitions 7F0→5D2, 7F0→5D1, 7F1→5D1, 7F1→5D0, 7F0→7F6 and 7F1→7F6 respectively. The experimental oscillator strengths with and without thermal corrections have been evaluated using absorption spectra. Judd-Ofelt (JO) intensity parameters (Ω2 and Ω4) have been evaluated from the photoluminescence spectra of all the glasses. PL spectra of all the glasses have been recorded at excitation wavelengths 395 nm (conventional excitation source) and 410 nm (diode laser) to observe the intensity variation in the PL spectra. All the spectra consists of five emission peaks corresponding to the transitions 5D0→7FJ (J = 0, 1, 2, 3 and 4). Surprisingly no concentration quenching is observed on PL spectra. Among all the glasses the glass with 2.0 mol% of Eu3+ ion concentration possesses maximum intensity for the transition 5D0→7F2 (612 nm) in bright red region. The JO parameters derived from the photoluminescence spectra have been used to evaluate the essential radiative properties such as transition probability (A), radiative lifetime (τR), branching ratio (βR) and peak stimulated emission cross-section (σse) for the 5D0→7FJ (J = 0, 1, 2, 3 and 4) transitions of the Eu3+ ions. The decay rates of the 5D0 fluorescent level of Eu3+ ions in the title glasses are found to be single exponential for all the studied Eu3+ ion concentrations. A marginal increase in lifetime of the 5D0 level has been noticed with increase in Eu3+ ion concentration from 0.1 mol% to 2.0 mol%. Among all the glasses, the glass with 2.0 mol% of Eu3+ ion concentration possesses maximum values of branching ratio, stimulated emission cross-section and quantum efficiency for the transition 5D0→7F2 (612 nm) in bright red region. The color chromaticity coordinates are also evaluated to confirm the reddish luminescence from these glasses. These color coordinates exactly fall in the bright red region. Confocal images also recorded to confirm reddish luminescence from these glasses. From all the obtained results in the present study, it is suggested that the glass with 2.0 mol% of Eu3+ ion concentration is suitable to emit bright red color laser.

Keywords: Europium, Judd-Ofelt parameters, laser, luminescence

Procedia PDF Downloads 213

Authors: María Canal-Rodríguez, María Arnaiz, Natalia Rey-Raap, Ana Arenillas, Jon Ajuria

Abstract:

The constant demand of electrical energy, as well as the increase in environmental concern, lead to the necessity of investing in clean and eco-friendly energy sources that implies the development of enhanced energy storage devices. Li-ion batteries (LIBs) and Electrical double layer capacitors (EDLCs) are the most widespread energy systems. Batteries are able to storage high energy densities contrary to capacitors, which main strength is the high-power density supply and the long cycle life. The combination of both technologies gave rise to Li-ion capacitors (LICs), which offers all these advantages in a single device. This is achieved combining a capacitive, supercapacitor-like positive electrode with a faradaic, battery-like negative electrode. Due to the abundance and affordability, dual carbon-based LICs are nowadays the common technology. Normally, an Active Carbon (AC) is used as the EDLC like electrode, while graphite is the material commonly employed as anode. LICs are potential systems to be used in applications in which high energy and power densities are required, such us kinetic energy recovery systems. Although these devices are already in the market, some drawbacks like the limited power delivered by graphite or the energy limiting nature of AC must be solved to trigger their used. Focusing on the anode, one possibility could be to replace graphite with Hard Carbon (HC). The better rate capability of the latter increases the power performance of the device. Moreover, the disordered carbonaceous structure of HCs enables storage twice the theoretical capacity of graphite. With respect to the cathode, the ACs are characterized for their high volume of micropores, in which the charge is storage. Nevertheless, they normally do not show mesoporous, which are really important mainly at high C-rates as they act as transport channels for the ions to reach the micropores. Usually, the porosity of ACs cannot be tailored, as it strongly depends on the precursor employed to get the final carbon. Moreover, they are not characterized for having a high electrical conductivity, which is an important characteristic to get a good performance in energy storage applications. A possible candidate to substitute ACs are carbon aerogels (CAs). CAs are materials that combine a high porosity with great electrical conductivity, opposite characteristics in carbon materials. Furthermore, its porous properties can be tailored quite accurately according to with the requirements of the application. In the present study, CAs with controlled porosity were obtained from polymerization of resorcinol and formaldehyde by microwave heating. Varying the synthesis conditions, mainly the amount of precursors and pH of the precursor solution, carbons with different textural properties were obtained. The way the porous characteristics affect the performance of the cathode was studied by means of a half-cell configuration. The material with the best performance was evaluated as cathode in a LIC versus a hard carbon as anode. An analogous full LIC made by a high microporous commercial cathode was also assembled for comparison purposes.

Keywords: li-ion capacitors, energy storage, tailored porosity, carbon aerogels

Procedia PDF Downloads 135

Authors: Babak Sadeghi, Rony Snyders, Marie-Paule.Delplancke-Ogletree

Abstract:

Nitrogen fixation (NF) is one of the crucial industrial processes. Many attempts have been made in order to artificially fix nitrogen, and among them, the Haber-Bosch’s (H-B) process is widely used. However, it presents two major drawbacks: huge fossil feedstock consumption and noticeable greenhouse gases emission. It is, therefore, necessary to develop alternatives. Plasma technology, as an inherent “green” technology, is considered to have a great potential for reducing the environmental impacts and improving the energy efficiency of the NF process. In this work, we have studied the catalyst assisted microwave plasma for NF application. Heterogeneous catalysts of MoO₃, with various loads 0, 5, 10, 20, and 30 wt%, supported on γ-alumina were prepared by conventional wet impregnation. Crystallinity, surface area, pore size, and microstructure were obtained by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) adsorption isotherm, Scanning electron microscopy (SEM), and Transmission electron microscopy (TEM). The XRD patterns of calcined alumina confirm the γ- phase. Characteristic picks of MoO₃ could not be observed for low loads (< 20 wt%), likely indicating a high dispersion of metal oxide over the support. The specific surface area along with pores size are decreasing with increasing calcination temperature and MoO₃ loading. The MoO₃ loading does not modify the microstructure. TEM and SEM results for loading inferior to 20 wt% are coherent with a monolayer of MoO₃ on the support as proposed elsewhere. For loading of 20 wt% and more, TEM and Electron diffraction (ED) show nanocrystalline ₃-D MoO₃ particles. The catalytic performances of these catalysts were investigated in the post-discharge of a microwave plasma for NOx formation from N₂/O₂ mixtures. The plasma is sustained by a surface wave launched in a quartz tube via a surfaguide supplied by a 2.45 GHz microwave generator in pulse mode. In-situ identification and quantification of the products were carried out by Fourier-transform infrared spectroscopy (FTIR) in the post-discharge region. FTIR analysis of the exhausted gas reveal NO and NO₂ bands in presence of catalyst while only NO band were assigned without catalyst. On the other hand, in presence of catalyst, a 10% increase of NOₓ formation and of 20% increase in energy efficiency are observed.

Keywords: γ-Al2O₃-MoO₃, µ-waveplasma, N2 fixation, Plasma-catalysis, Plasma diagnostic

Procedia PDF Downloads 148

Authors: Bao Chen, Frederic Kuznik, Matthieu Horgnies, Kevyn Johannes, Vincent Morin, Edouard Gengembre

Abstract:

The contradiction between energy consumption, environment protection, and social development is increasingly intensified during recent decade years. At the same time, as avoiding fossil-fuels-thirsty, people turn their view on the renewable green energy, such as solar energy, wind power, hydropower, etc. However, due to the unavoidable mismatch on geography and time for production and consumption, energy storage seems to be one of the most reasonable solutions to enlarge the use of renewable energies. Thermal energy storage (TES), a branch of energy storage solution, mainly concerns the capture, storage and consumption of thermal energy for later use in different scales (individual house, apartment, district, and city). In TES research field, sensible heat and latent heat storage have been widely studied and presented at an advanced stage of development. Compared with them, thermochemical energy storage is still at initial phase but provides a relatively higher theoretical energy density and a long shelf life without heat dissipation during storage. Among thermochemical energy storage materials, inorganic pure or composite compounds like micro-porous silica gel, SrBr₂ hydrate and MgSO₄-Zeolithe have been reported as promising to be integrated into thermal energy storage systems. However, the cost of these materials, one of main obstacles, may hinder the wide use of energy storage systems in real application scales (individual house, apartment, district and even city). New studies on ettringite show promising application for thermal energy storage since its high energy density and large resource from cementitious materials. Ettringite, or calcium trisulfoaluminate hydrate, of which chemical formula is 3CaO∙Al₂O₃∙3CaSO₄∙32H₂O, or C₆AS̅₃H₃₂ as known in cement chemistry notation, is one of the most important members of AFt group. As a common compound in hydrated cements, ettringite has been widely studied for its performances in construction but barely known as a thermochemical material. For this study, we summarize available data about the structure and properties of ettringite and its metastable phase (meta-ettringite), including the processes of hydration, thermal conversion and carbonation durability for thermal energy storage.

Keywords: building materials, ettringite, meta-ettringite, thermal energy storage

Procedia PDF Downloads 190

Authors: R. P. Naik, A. K. Rakshit

Abstract:

In recent years, with the rapid development in science and technology, people have increasing requirements on uses of clothing for new functions, which contributes to opportunities for further development and incorporation of new technologies along with novel materials. In this context, textiles are of fast decalescence or fast heat radiation media as per as comfort accountability of textile articles are concern. The microstructure and texture of textiles play a vital role in determining the heat-moisture comfort level of the human body because clothing serves as a barrier to the outside environment and a transporter of heat and moisture from the body to the surrounding environment to keep thermal balance between body heat produced and body heat loss. The main bottleneck which is associated with textile materials to be successful as thermal insulation materials can be enumerated as; firstly, high loft or bulkiness of material so as to provide predetermined amount of insulation by ensuring sufficient trapping of air. Secondly, the insulation depends on forced convection; such convective heat loss cannot be prevented by textile material. Third is that the textile alone cannot reach the level of thermal conductivity lower than 0.025 W/ m.k of air. Perhaps, nano-fibers can do so, but still, mass production and cost-effectiveness is a problem. Finally, such high loft materials for thermal insulation becomes heavier and uneasy to manage especially when required to carry over a body. The proposed works aim at developing lightweight effective thermal insulation textiles in combination with nanoporous silica-gel which provides the fundamental basis for the optimization of material properties to achieve good performance of the clothing system. This flexible nonwoven silica-gel composites fabric in intact monolith was successfully developed by reinforcing SiO2-gel in thermal bonded nonwoven fabric via sol-gel processing. Ambient Pressure Drying method is opted for silica gel preparation for cost-effective manufacturing. The formed structure of the nonwoven / SiO₂ -gel composites were analyzed, and the transfer properties were measured. The effects of structure and fibre on the thermal properties of the SiO₂-gel composites were evaluated. Samples are then tested against untreated samples of same GSM in order to study the effect of SiO₂-gel application on various properties of nonwoven fabric. The nonwoven fabric composites reinforced with aerogel showed intact monolith structure were also analyzed for their surface structure, functional group present, microscopic images. Developed product reveals a significant reduction in pores' size and air permeability than the conventional nonwoven fabric. Composite made from polyester fibre with lower GSM shows lowest thermal conductivity. Results obtained were statistically analyzed by using STATISTICA-6 software for their level of significance. Univariate tests of significance for various parameters are practiced which gives the P value for analyzing significance level along with that regression summary for dependent variable are also studied to obtain correlation coefficient.

Keywords: silica-gel, heat insulation, nonwoven fabric, thermal barrier clothing

Procedia PDF Downloads 86

Authors: Amit Mallik, Anil K. Barik, Biswajit Pal

Abstract:

The galloping advancement of research work on glass-ceramics stems from their wide applications in electronic industry and also to some extent in application oriented medical dentistry. TiO2, even in low concentration has been found to strongly influence the physical and mechanical properties of the glasses. Glass-ceramics is a polycrystalline ceramic material produced through controlled crystallization of glasses. Crystallization is accomplished by subjecting the suitable parent glasses to a regulated heat treatment involving the nucleation and growth of crystal phases in the glass. Mica glass-ceramics is a new kind of glass-ceramics based on the system SiO2•MgO•K2O•F. The predominant crystalline phase is synthetic fluormica, named fluorophlogopite. Mica containing glass-ceramics flaunt an exceptional feature of machinability apart from their unique thermal and chemical properties. Machinability arises from the randomly oriented mica crystals with a 'house of cards' microstructures allowing cracks to propagate readily along the mica plane but hindering crack propagation across the layers. In the present study, we have systematically investigated the crystallization, microstructure and mechanical behavior of barium fluorophlogopite mica-containing glass-ceramics of composition BaO•4MgO•Al2O3•6SiO2•2MgF2 nucleated by addition of 2, 4, 6 and 8 wt% TiO2. The glass samples were prepared by the melting technique. After annealing, different batches of glass samples for nucleation were fired at 730°C (2wt% TiO2), 720°C (4 wt% TiO2), 710°C (6 wt% TiO2) and 700°C (8 wt% TiO2) batches respectively for 2 h and ultimately heated to corresponding crystallization temperatures. The glass batches were analyzed by differential thermal analysis (DTA) and x-ray diffraction (XRD), scanning electron microscopy (SEM) and micro hardness indenter. From the DTA study, it is found that the fluorophlogopite mica crystallization exotherm appeared in the temperature range 886–903°C. Glass transition temperature (Tg) and crystallization peak temperature (Tp) increased with increasing TiO2 content up to 4 wt% beyond this weight% the glass transition temperature (Tg) and crystallization peak temperature (Tp) start to decrease with increasing TiO2 content up to 8 wt%. Scanning electron microscopy confirms the development of an interconnected ‘house of cards’ microstructure promoted by TiO2 as a nucleating agent. The increase in TiO2 content decreases the vicker’s hardness values in glass-ceramics.

Keywords: crystallization, fluormica glass, ‘house of cards’ microstructure, hardness

Procedia PDF Downloads 216

Authors: Ayman Hijazi, Witold Kwapinski, J. J. Leahy

Abstract:

Finding a sustainable alternative energy to fossil fuel is an urgent need as various environmental challenges in the world arise. Therefore, formic acid (FA) decomposition has been an attractive field that lies at the center of biomass platform, comprising a potential pool of hydrogen energy that stands as a new energy vector. Liquid FA features considerable volumetric energy density of 6.4 MJ/L and a specific energy density of 5.3 MJ/Kg that qualifies it in the prime seat as an energy source for transportation infrastructure. Additionally, the increasing research interest in FA decomposition is driven by the need of in-situ H2 production, which plays a key role in the hydrogenation reactions of biomass into higher value components. It is reported elsewhere in literature that catalytic decomposition of FA is usually performed in poorly designed setup using simple glassware under magnetic stirring, thus demanding further energy investment to retain the used catalyst. it work suggests an approach that integrates designing a novel catalyst featuring magnetic property with a robust setup that minimizes experimental & measurement discrepancies. One of the most prominent active species for dehydrogenation/hydrogenation of biomass compounds is palladium. Accordingly, we investigate the potential of engrafting palladium metal onto functionalized magnetic nanoparticles as a heterogeneous catalyst to favor the production of CO-free H2 gas from FA. Using ordinary magnet to collect the spent catalyst renders core-shell magnetic nanoparticles as the backbone of the process. Catalytic experiments were performed in a jacketed batch reactor equipped with an overhead stirrer under inert medium. Through a novel approach, FA is charged into the reactor via high-pressure positive displacement pump at steady state conditions. The produced gas (H2+CO2) was measured by connecting the gas outlet to a measuring system based on the amount of the displaced water. The novelty of this work lies in designing a very responsive catalyst, pumping consistent amount of FA into a sealed reactor running at steady state mild temperatures, and continuous gas measurement, along with collecting the used catalyst without the need for centrifugation. Catalyst characterization using TEM, XRD, SEM, and CHN elemental analyzer provided us with details of catalyst preparation and facilitated new venues to alter the nanostructure of the catalyst framework. Consequently, the introduction of amine groups has led to appreciable improvements in terms of dispersion of the doped metals and eventually attaining nearly complete conversion (100%) of FA after 7 hours. The relative importance of the process parameters such as temperature (35-85°C), stirring speed (150-450rpm), catalyst loading (50-200mgr.), and Pd doping ratio (0.75-1.80wt.%) on gas yield was assessed by a Taguchi design-of-experiment based model. Experimental results showed that operating at lower temperature range (35-50°C) yielded more gas while the catalyst loading and Pd doping wt.% were found to be the most significant factors with a P-values 0.026 & 0.031, respectively.

Keywords: formic acid decomposition, green catalysis, hydrogen, mesoporous silica, process optimization, nanoparticles

Procedia PDF Downloads 18

Authors: H. M. Nanjundaswamy, S. K. Nath, S. Ray

Abstract:

TiO₂ particles have been added in molten aluminium to result in aluminium based cast Al/Al₃Ti-Al₂O₃ composite, which has been added then to molten magnesium to synthesize magnesium based cast Mg-Al/Al₃Ti-Al₂O₃ composite. The nominal compositions in terms of Mg, Al, and TiO₂ contents in the magnesium based composites are Mg-9Al-0.6TiO₂, Mg-9Al-0.8TiO₂, Mg-9Al-1.0TiO₂ and Mg-9Al-1.2TiO₂ designated respectively as MA6T, MA8T, MA10T and MA12T. The microstructure of the cast magnesium based composite shows grayish rods of intermetallics Al₃Ti, inherited from aluminium based composite but these rods, on hot forging, breaks into smaller lengths decreasing the average aspect ratio (length to diameter) from 7.5 to 3.0. There are also cavities in between the broken segments of rods. β-phase in cast microstructure, Mg₁₇Al₁₂, dissolves during heating prior to forging and re-precipitates as relatively finer particles on cooling. The amount of β-phase also decreases on forging as segregation is removed. In both the cast and forged composite, the Brinell hardness increases rapidly with increasing addition of TiO₂ but the hardness is higher in forged composites by about 80 BHN. With addition of higher level of TiO₂ in magnesium based cast composite, yield strength decreases progressively but there is marginal increase in yield strength over that of the cast Mg-9 wt. pct. Al, designated as MA alloy. But the ultimate tensile strength (UTS) in the cast composites decreases with the increasing particle content indicating possibly an early initiation of crack in the brittle inter-dendritic region and their easy propagation through the interfaces of the particles. In forged composites, there is a significant improvement in both yield strength and UTS with increasing TiO₂ addition and also, over those observed in their cast counterpart, but at higher addition it decreases. It may also be noted that as in forged MA alloy, incomplete recovery of forging strain increases the strength of the matrix in the composites and the ductility decreases both in the forged alloy and the composites. Initiation fracture toughness, J_IC, decreases drastically in cast composites compared to that in MA alloy due to the presence of intermetallic Al₃Ti and Al₂O₃ particles in the composite. There is drastic reduction of J_IC on forging both in the alloy and the composites, possibly due to incomplete recovery of forging strain in both as well as breaking of Al₃Ti rods and the voids between the broken segments of Al₃Ti rods in composites. The ratio of tearing modulus to elastic modulus in cast composites show higher ratio, which increases with the increasing TiO₂ addition. The ratio decreases comparatively more on forging of cast MA alloy than those in forged composites.

Keywords: composite, fracture toughness, forging, tensile properties

Procedia PDF Downloads 221

Authors: Fatima Khurshid, Noor Ul Ain, Syed Abdul Rehman Kashif, Zainab Riaz, Abdullah Usman Khan, Muhammad Imran

Abstract:

As the world is moving towards extra-high voltage (EHV) and ultra-high voltage (UHV) power systems, the performance requirements of power transformers are becoming crucial to the system reliability and security. With the transformers being an essential component of a power system, low health index of transformers poses greater risks for safe and reliable operation. Therefore, to meet the rising demands of the power system and transformer performance, researchers are being prompted to provide solutions for enhanced thermal and electrical properties of transformers. This paper proposes an approach to improve the health index of a transformer by using nano-technology in conjunction with bio-degradable oils. Vegetable oils can serve as potential dielectric fluid alternatives to the conventional mineral oils, owing to their numerous inherent benefits; namely, higher fire and flashpoints, and being environment-friendly in nature. Moreover, the addition of nanoparticles in the dielectric fluid further serves to improve the dielectric strength of the insulation medium. In this research, using the finite element method (FEM) in COMSOL Multiphysics environment, and a 2D space dimension, three different oil samples have been modelled, and the electric field distribution is computed for each sample at various electric potentials, i.e., 90 kV, 100 kV, 150 kV, and 200 kV. Furthermore, each sample has been modified with the addition of nanoparticles of different radii (50 nm and 100 nm) and at different interparticle distance (5 mm and 10 mm), considering an instant of time. The nanoparticles used are non-conductive and have been modelled as alumina (Al₂O₃). The geometry has been modelled according to IEC standard 60897, with a standard electrode gap distance of 25 mm. For an input supply voltage of 100 kV, the maximum electric field stresses obtained for the samples of synthetic vegetable oil, olive oil, and mineral oil are 5.08 ×10⁶ V/m, 5.11×10⁶ V/m and 5.62×10⁶ V/m, respectively. It is observed that for the unmodified samples, vegetable oils have a greater dielectric strength as compared to the conventionally used mineral oils because of their higher flash points and higher values of relative permittivity. Also, for the modified samples, the addition of nanoparticles inhibits the streamer propagation inside the dielectric medium and hence, serves to improve the dielectric properties of the medium.

Keywords: dielectric strength, finite element method, health index, nanotechnology, streamer propagation

Procedia PDF Downloads 118

Authors: Ayman Hijazi, Witold Kwapinski, J. J. Leahy

Abstract:

Finding a sustainable alternative energy to fossil fuel is an urgent need as various environmental challenges in the world arise. Therefore, formic acid (FA) decomposition has been an attractive field that lies at the center of the biomass platform, comprising a potential pool of hydrogen energy that stands as a distinct energy vector. Liquid FA features considerable volumetric energy density of 6.4 MJ/L and a specific energy density of 5.3 MJ/Kg that qualifies it in the prime seat as an energy source for transportation infrastructure. Additionally, the increasing research interest in FA decomposition is driven by the need for in-situ H₂ production, which plays a key role in the hydrogenation reactions of biomass into higher-value components. It is reported elsewhere in the literature that catalytic decomposition of FA is usually performed in poorly designed setups using simple glassware under magnetic stirring, thus demanding further energy investment to retain the used catalyst. Our work suggests an approach that integrates designing a distinct catalyst featuring magnetic properties with a robust setup that minimizes experimental & measurement discrepancies. One of the most prominent active species for the dehydrogenation/hydrogenation of biomass compounds is palladium. Accordingly, we investigate the potential of engrafting palladium metal onto functionalized magnetic nanoparticles as a heterogeneous catalyst to favor the production of CO-free H₂ gas from FA. Using an ordinary magnet to collect the spent catalyst renders core-shell magnetic nanoparticles as the backbone of the process. Catalytic experiments were performed in a jacketed batch reactor equipped with an overhead stirrer under an inert medium. Through a distinct approach, FA is charged into the reactor via a high-pressure positive displacement pump at steady-state conditions. The produced gas (H₂+CO₂) was measured by connecting the gas outlet to a measuring system based on the amount of the displaced water. The uniqueness of this work lies in designing a very responsive catalyst, pumping a consistent amount of FA into a sealed reactor running at steady-state mild temperatures, and continuous gas measurement, along with collecting the used catalyst without the need for centrifugation. Catalyst characterization using TEM, XRD, SEM, and CHN elemental analyzer provided us with details of catalyst preparation and facilitated new venues to alter the nanostructure of the catalyst framework. Consequently, the introduction of amine groups has led to appreciable improvements in terms of dispersion of the doped metals and eventually attaining nearly complete conversion (100%) of FA after 7 hours. The relative importance of the process parameters such as temperature (35-85°C), stirring speed (150-450rpm), catalyst loading (50-200mgr.), and Pd doping ratio (0.75-1.80wt.%) on gas yield was assessed by a Taguchi design-of-experiment based model. Experimental results showed that operating at a lower temperature range (35-50°C) yielded more gas, while the catalyst loading and Pd doping wt.% were found to be the most significant factors with P-values 0.026 & 0.031, respectively.

Keywords: formic acid decomposition, green catalysis, hydrogen, mesoporous silica, process optimization, nanoparticles

Procedia PDF Downloads 16

Authors: Trevor C. Brown, David J. Miron

Abstract:

Gas-solid physical adsorption methods are central to the characterization and optimization of the effective surface area, pore size and porosity for applications such as heterogeneous catalysis, and gas separation and storage. Properties such as adsorption uptake, capacity, equilibrium constants and Gibbs free energy are dependent on the composition and structure of both the gas and the adsorbent. However, challenges remain, in accurately calculating these properties from experimental data. Gas adsorption experiments involve measuring the amounts of gas adsorbed over a range of pressures under isothermal conditions. Various constant-parameter models, such as Langmuir and Brunauer-Emmett-Teller (BET) theories are used to provide information on adsorbate and adsorbent properties from the isotherm data. These models typically do not provide accurate interpretations across the full range of pressures and temperatures. The Langmuir adsorption isotherm is a simple approximation for modelling equilibrium adsorption data and has been effective in estimating surface areas and catalytic rate laws, particularly for high surface area solids. The Langmuir isotherm assumes the systematic filling of identical adsorption sites to a monolayer coverage. The BET model is based on the Langmuir isotherm and allows for the formation of multiple layers. These additional layers do not interact with the first layer and the energetics are equal to the adsorbate as a bulk liquid. This BET method is widely used to measure the specific surface area of materials. Both Langmuir and BET models assume that the affinity of the gas for all adsorption sites are identical and so the calculated adsorbent uptake at the monolayer and equilibrium constant are independent of coverage and pressure. Accurate representations of adsorption data have been achieved by extending the Langmuir and BET models to include pressure-varying uptake capacities and equilibrium constants. These parameters are determined using a novel regression technique called flexible least squares for time-varying linear regression. For isothermal adsorption the adsorption parameters are assumed to vary slowly and smoothly with increasing pressure. The flexible least squares for pressure-varying linear regression (FLS-PVLR) approach assumes two distinct types of discrepancy terms, dynamic and measurement for all parameters in the linear equation used to simulate the data. Dynamic terms account for pressure variation in successive parameter vectors, and measurement terms account for differences between observed and theoretically predicted outcomes via linear regression. The resultant pressure-varying parameters are optimized by minimizing both dynamic and measurement residual squared errors. Validation of this methodology has been achieved by simulating adsorption data for n-butane and isobutane on activated carbon at 298 K, 323 K and 348 K and for nitrogen on mesoporous alumina at 77 K with pressure-varying Langmuir and BET adsorption parameters (equilibrium constants and uptake capacities). This modeling provides information on the adsorbent (accessible surface area and micropore volume), adsorbate (molecular areas and volumes) and thermodynamic (Gibbs free energies) variations of the adsorption sites.

Keywords: Langmuir adsorption isotherm, BET adsorption isotherm, pressure-varying adsorption parameters, adsorbate and adsorbent properties and energetics

Procedia PDF Downloads 194

Authors: Mantas Sriubas, Kristina Bockute, Darius Virbukas, Giedrius Laukaitis

Abstract:

In this work, the doped TiO2 (dopants – Ca, Mg) was investigated. The comparison between the physical vapour deposition methods as electron beam vapour deposition and magnetron sputtering was performed and the structural and electrical properties of the formed thin films were investigated. Thin films were deposited on different type of substrates: SiO2, Alloy 600 (Fe-Ni-Cr) and Al2O3 substrates. The structural properties were investigated using Ambios XP-200 profilometer, scanning electron microscope (SEM) Hitachi S-3400N, X-ray energy-dispersive spectroscope (EDS) Quad 5040 (Bruker AXS Microanalysis GmbH), X-ray diffractometer (XRD) D8 Discover (Bruker AXS GmbH) with glancing angles focusing geometry in a 20 – 70° range using the Cu Kα1 λ = 0.1540562 nm radiation). The impedance spectroscopy measurements were performed using Probostat® (NorECs AS) measurement cell in the frequency range from 10-1-106 Hz under reducing and oxidizing conditions in temperature range of 200 °C to 1200 °C. The investigation of the e-beam deposited Ca and Mg doped-TiO2 thin films shows that the thin films are dense without any visible pores and cavities and the thin films grow in zone T according Barna-Adamik SZM. Substrate temperature was kept 600 °C during the deposition and Ts/Tm ≈ 0.32 (substrate temperature (Ts) and coating material melting temperature (Tm)). The surface diffusion is high however, the grain boundary migration is strongly limited at this temperature. This means that structure is inhomogeneous and the columnar structure is mostly visible in the upper part of the films. According to XRD, the increasing of the Ca dopants’ concentration increases the crystallinity of the formed thin films and the crystallites size increase linearly and Ca dopants act as prohibitors. Thin films are comprised of anatase TiO2 phase with an exception of 2 % Ca doped TiO2, where a small peak of Ca arise. In the case of Mg doped-TiO2 the intensities of the XRD peaks decreases with increasing Mg molar concentration. It means that there are less diffraction planes of the particular orientation in thin films with higher impurities concentration. Thus, the crystallinity decreases with increasing Mg concentration and Mg dopants act as inhibitors. The impedance measurements show that the dopants changed the conductivity of the formed thin films. The conductivity varies from 10-3 S/cm to 10-4 S/cm at 800 °C under wet reducing conditions. The microstructure of the magnetron sputtered thin TiO2 films is different comparing to the thin films deposited using e-beam deposition therefore influencing other structural and electrical properties.

Keywords: electrical properties, electron beam deposition, magnetron sputtering, microstructure, titanium dioxide

Procedia PDF Downloads 271

Authors: Chetna Mohabeer, Luis Reyes, Lokmane Abdelouahed, Bechara Taouk

Abstract:

In the transition to sustainability and the increasing use of renewable energy, hydrogen will play a key role as an energy carrier. Biomass has the potential to accelerate the realization of hydrogen as a major fuel of the future. Pyro-gasification allows the conversion of organic matter mainly into synthesis gas, or “syngas”, majorly constituted by CO, H2, CH4, and CO2. A second, condensable fraction of biomass pyro-gasification products are “tars”. Under certain conditions, tars may decompose into hydrogen and other light hydrocarbons. These conditions include two types of cracking: homogeneous cracking, where tars decompose under the effect of temperature ( > 1000 °C), and heterogeneous cracking, where catalysts such as olivine, dolomite or biochar are used. The latter process favors cracking of tars at temperatures close to pyro-gasification temperatures (~ 850 °C). Pyro-gasification of biomass coupled with water-gas shift is the most widely practiced process route for biomass to hydrogen today. In this work, an innovating solution will be proposed for this conversion route, in that all the pyro-gasification products, not only methane, will undergo processes that aim to optimize hydrogen production. First, a heterogeneous cracking step was included in the reaction scheme, using biochar (remaining solid from the pyro-gasification reaction) as catalyst and CO2 and H2O as gasifying agents. This process was followed by a catalytic steam methane reforming (SMR) step. For this, a Ni-based catalyst was tested under different reaction conditions to optimize H2 yield. Finally, a water-gas shift (WGS) reaction step with a Fe-based catalyst was added to optimize the H2 yield from CO. The reactor used for cracking was a fluidized bed reactor, and the one used for SMR and WGS was a fixed bed reactor. The gaseous products were analyzed continuously using a µ-GC (Fusion PN 074-594-P1F). With biochar as bed material, it was seen that more H2 was obtained with steam as a gasifying agent (32 mol. % vs. 15 mol. % with CO2 at 900 °C). CO and CH4 productions were also higher with steam than with CO2. Steam as gasifying agent and biochar as bed material were hence deemed efficient parameters for the first step. Among all parameters tested, CH4 conversions approaching 100 % were obtained from SMR reactions using Ni/γ-Al2O3 as a catalyst, 800 °C, and a steam/methane ratio of 5. This gave rise to about 45 mol % H2. Experiments about WGS reaction are currently being conducted. At the end of this phase, the four reactions are performed consecutively, and the results analyzed. The final aim is the development of a global kinetic model of the whole system in a multi-stage fluidized bed reactor that can be transferred on ASPEN PlusTM.

Keywords: multi-staged fluidized bed reactor, pyro-gasification, steam methane reforming, water-gas shift

Procedia PDF Downloads 107