World Academy of Science, Engineering and Technology

Authors: Yuan Yan

Abstract:

Interlayer interactions or hybridization in van der Waals (vdW) heterostructures of two-dimensional (2D) materials significantly influence their physical characteristics, including layer-dependent electronic and vibrational structures, magic-angle superconductivity, interlayer antiferromagnetism, and interlayer excitons. These interactions are sensitive to a set of interdependent and externally tunable parameters. To fully exploit the potential of these materials, it is crucial to understand the physical origins of interlayer interaction and hybridization. Traditional theories often attribute these interactions to the sharing of electrons via p orbital lone pairs or π electrons, based on the octet rule, which posits that p electrons are the primary occupants of the outermost atomic shells, except in hydrogen. However, our study challenges this prevailing belief. Through geometry-based analysis, we conducted a high-throughput screening of the Materials Project database and identified 1,623 layered materials. By examining the atomic structure and bonding characteristics of surface atoms, we demonstrate that s-orbital lone pairs can also drive interlayer interactions in two-dimensional materials. Using density functional theory, we further analyzed charge distribution and electronic localization. The crystal field and inert pair effect induce a Stark-like phenomenon, leading to energy level splitting and the formation of directional electron clouds. This allows these electrons to directly participate in the hybridization of interlayer wavefunctions without forming chemical bonds. it findings expand the understanding of interlayer interactions, revealing new mechanisms that govern these properties and providing a theoretical foundation for manipulating interlayer phenomena in 2D materials.

Keywords: interlayer interaction, nanomaterials, 2D materials, van der waals, heterostructures

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Authors: Joao Paulo De Oliveira Paschoal, Andre Victor Rodrigues Dantas, Fernando Almeida Da Silva Fernandes, Eugenio Jose Zoqui

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With the adoption of High Pressure Die Casting technologies for the production of automotive bodies by the famous Giga Castings, the technology of processing metal alloys in the semi-solid state (SSM) becomes interesting because it allows for higher product quality, such as lower porosity and shrinkage voids. However, the alloys currently processed are derived from the foundry industry and are based on the Al-Si-(Cu-Mg) system. High-strength alloys, such as those of the Al-Zn-Mg-Cu system, are not usually processed, but the benefits of using this system, which is susceptible to heat treatments, can be associated with the advantages obtained by processing in the semi-solid state, promoting new possibilities for production routes and improving product performance. The current work proposes a new range of alloys to be processed in the semi-solid state through the modification of aluminum alloys of the Al-Zn-Mg-Cu system by the in-situ formation of Al3Ti intermetallic. Such alloys presented the thermodynamic stability required for semi-solid processing, with a sensitivity below 0.03(Celsius degrees * -1), in a wide temperature range. Furthermore, these alloys presented high hardness after aging heat treatment, reaching 190HV. Therefore, they are excellent candidates for the manufacture of parts that require low levels of defects and high mechanical strength.

Keywords: aluminum alloys, semisolid metals processing, intermetallics, heat treatment, titanium aluminide

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Authors: Maciej Życki, Anna Kowalik-klimczak, Monika Łożyńska, Wioletta Barszcz, Jolanta Drabik Anna Kowalik-klimczak

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The rapidly changing fashion trends generate huge amounts of leather and textile waste globally. The complexity of these types of waste makes recycling difficult in economic terms. Pyrolysis is suggested for this purpose, which transforms heterogeneous and complex waste into added-value products e.g. active carbons and soil fertilizer. The possibility of using pyrolysis for the valorization of leather and textile waste has been analyzed in this paper. In the first stage, leather and textile waste were subjected to TG/DTG thermogravimetric and DSC calorimetric analysis. These analyses provided basic information about thermochemical transformations and degradation rates during the pyrolysis of these types of waste and enabled the selection of the pyrolysis temperature. In the next stage, the effect of gas type using pyrolysis was investigated on the physicochemical properties, composition, structure, and formation of the specific surfaces of carbonized materials produced by means of a thermal treatment without oxygen access to the reaction chamber. These studies contribute some data about the thermal management and pyrolytic processing of leather and textile waste into useful carbonized materials, according to the circular economy model.

Keywords: pyrolysis, leather and textiles waste, composition and structure of carbonized materials, valorisation of waste, circular economy model

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Authors: Jerzy Smardzewski

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Structures with negative Poisson's ratios are called auxetic. They are characterized by better mechanical properties than conventional structures, especially shear strength, the ability to better absorb energy and increase strength during bending, especially in sandwich panels. Commonly used paper cores of cellular boards are made of hexagonal cells. With isotropic facings, these cells provide isotropic properties of the entire furniture board. Shelves made of such panels with a thickness similar to standard chipboards do not provide adequate stiffness and strength of the furniture. However, it is possible to transform the shape of hexagonal cells into polyhedral auxetic cells that improve the mechanical properties of the core. The work aimed to transform the hexagonal cells of the paper core into auxetic cells and determine their basic mechanical properties. Using numerical methods, it was decided to design the most favorable proportions of cells distinguished by the lowest Poisson's ratio and the highest modulus of linear elasticity. Standard cores for cellular boards commonly used to produce 34 mm thick furniture boards were used for the tests. Poisson's ratios, bending strength, and linear elasticity moduli were determined for such cores and boards. Then, the cells were transformed into auxetic structures, and analogous cellular boards were made for which mechanical properties were determined. The results of numerical simulations for which the variable parameters were the dimensions of the cell walls, wall inclination angles, and relative cell density were presented in the further part of the paper. Experimental tests and numerical simulations showed the beneficial effect of auxeticization on the mechanical quality of furniture panels. They allowed for the selection of the optimal shape of auxetic core cells.

Keywords: auxetics, honeycomb, panels, simulation, experiment

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Authors: Aguasanta M. Sarmiento, Jose Miguel Davila, Juan Carlos Fortes, Maria Luisa de la Torre

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Acid mine drainage (AMD) is an acidic leachate with high levels of metals and sulphates in solution, which seriously affects the durability and strength of metallic materials used in the construction of structural and mechanical components. This paper presents the results of the evolution over time of the reduction in tensile strength and defects in AISI 304 stainless steel in contact with acid mine drainage. For this purpose, a total of 30 bars with a diameter of 8 mm and a length of 14 cm were placed transversely in the course of a stream contaminated by AMD from the sulphide mines of the Iberian Pyritic Belt (SW Spain). This stream has average pH values of 2.6, a potential of 660 mV and average concentrations of 12 g/L of sulphates, 1.2 g/L of Fe, 191 mg/L of Zn, etc. Every two months of exposure, 6 stainless steel bars were extracted from the acid stream. They were subjected to surface roughness analysis carried out with the help of Mitutoyo Surftest SJ-210 surface roughness tester. The analysis was carried out at three different points on 5 specimens from each series. The average reading of each parameter is calculated in order to ensure the accuracy of the measurements and the surface coverage. Arithmetic mean roughness value (Ra), mean roughness depth (Rz) and root mean square roughness (Rq) were measured. Five specimens from each series were statically tensile tested using universal equipment (Servosis ME 403 of 200kN). The specimens were clamped at their ends with two grips for cylindrical sections, and the tensile force was applied at a constant speed of 0.5 kN/s, according to the requirements of standard UNE-EN ISO 6892-1: 2020. To determine the modulus of elasticity, limits close to 15% and 55% of the maximum load were used, depending on the course of each test. Field Emission Scanning Electron Microscopy (FESEM) was used to observe corrosion products and defects generated by exposure to AMD. Energy dispersive X-ray spectrometry (EDS) was used to analyze the chemical composition of the corrosion products formed. For this purpose, small pieces were cut from the resulting specimens, cleaned and embedded in epoxy resin. The results show that after only 5 months of exposure of AISI 304 stainless steel to the mining environment, the surface roughness increases significantly, with average depths almost 6 times greater than the initial one. Cracks are observed on the surface of the material, which increases in size with the time of exposure. A large number of grains with a composition of more than 57% Pb and 16% Sn can be observed inside these cracks. Tensile tests show a reduction in the resistance of this material after only two months of exposure. The results show the serious problems that would result from the use of this material for the use of mechanical components in a sulphide mining environment, not only because of the significant reduction in the lifetime of such components but also because of the implications for human safety.

Keywords: Acid mine drainage, Corrosion, Mechanical properties, Stainless steel

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Authors: Maria Luisa de la Torre, Javier Aroba, Jose Miguel Davila, Aguasanta M. Sarmiento

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Steel is one of the most widely used materials in polymetallic sulfide mining installations. One of the main problems suffered by these facilities is the economic losses due to the corrosion of this material, which is accelerated and aggravated by the contact with acid waters generated in these mines when sulfides come into contact with oxygen and water. This generation of acidic water, in turn, is accelerated by the presence of acidophilic bacteria. In order to gain a more detailed understanding of this corrosion process and the interaction between steel and acidic water, a laboratory experiment was carried out in which carbon steel plates were introduced into four different solutions for 27 days: distilled water (BK), which tried to assimilate the effect produced by rain on this material, an acid solution from a mine with a high Fe2+/Fe3+ (PO) content, another acid solution of water from another mine with a high Fe3+/Fe2+ (PH) content and, finally, one that reproduced the acid mine water with a high Fe2+/Fe3+ content but in which there were no bacteria (ST). Every 24 hours, physicochemical parameters were measured, and water samples were taken to carry out an analysis of the dissolved elements. The results of these measurements were processed using an explainable AI model based on fuzzy logic. It could be seen that, in all cases, there was an increase in pH, as well as in the concentrations of Fe and, in particular, Fe(II), as a consequence of the oxidation of the steel plates. Proportionally, the increase in Fe concentration was higher in PO and ST than in PH because Fe precipitates were produced in the latter. The rise of Fe(II) was proportionally much higher in PH, especially in the first hours of exposure, because it started from a lower initial concentration of this ion. Although to a lesser extent than in PH, the greater increase in Fe(II) also occurred faster in PO than in ST, a consequence of the action of the catalytic bacteria. On the other hand, Cu concentrations decreased throughout the experiment (with the exception of distilled water, which initially had no Cu, as a result of an electrochemical process that generates a precipitation of Cu together with Fe hydroxides. This decrease is lower in PH because the high total acidity keeps it in solution for a longer time. With the application of an artificial intelligence tool, it has been possible to evaluate the effects of steel corrosion in mining environments, corroborating and extending what was obtained by means of classical statistics.

Keywords: acid mine drainage, artificial intelligence, carbon steel, corrosion, fuzzy logic

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Authors: A. Pattulee, I. Lawan, N. Boonnao, R. Gholami, P. Rimdusit, S. Rimdusit

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Varied types and content of ultrafine vulcanized powdered natural rubbers (UFPNR) as toughening fillers of polybenzoxazine composite are investigated in this work. Four types of UFPNR were prepared by graft polymerization of acrylonitrile monomer (AN), styrene monomer (ST), styrene-acrylonitrile copolymer (ST/AN), and styrene-methyl methacrylate copolymer (ST/MMA) onto deproteinized natural rubber (DPNR). The solid UFPNR powders with different types of grafting were finally obtained by electron beam vulcanization and a spray-drying technique. Additionally, effects of various UFPNR contents (0, 5, 10, 15, 20, and 25 wt%) on toughness of polybenzoxazine composites were studied. It was observed that the UFPNR grafted with the styrene-methyl methacrylate copolymer (UFPNR-g-(PS-co-PMMA)) exhibited the most effective toughening agent for polybenzoxazine, whereas the rubber powder content of 25 wt% was found to be the optimal filler loading in enhancing the toughness of the resulting composite. The experimental results revealed an increase of 86% in toughness and 56% in impact strength at the above UFPNR-g- (PS-co-PMMA powdered rubber content. Interestingly, the utilization of the UFPNR-g-(PS-co-PMMA as toughening agent was found to increase thermal stability (degradation temperature at 5wt.% (Td5) and glass transition temperature (Tg) of the composite i.e. an increase of 8°C and 6 °C has been observed for the Td5 and Tg, respectively.

Keywords: natural rubber, ultrafine fully vulcanized powder rubber, polybenzoxazine, polymer composite, toughening

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Authors: Panyawutthi Rimdusit, Krittapas Charoensuk, Sarawut Rimdusit

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A biobased toughening filler for polylactic acid (PLA) based on natural rubber is developed in this work. Deproteinized natural rubber (DPNR) was modified by grafting polymerization with methyl methacrylate monomer (MMA) and further crosslinked by e-beam irradiation and spray drying process to achieve ultrafine full vulcanized powdered natural rubber grafted with polymethylmethacrylate (UFPNRg-PMMA) to solves in the challenges of incompatibility between natural rubber and PLA. Intriguingly, UFPNR-g-PMMA revealed outstanding and unique properties with minimal particle aggregation. The average particle size of rubber powder obtained from UFPNR-g-PMMA at PMMA grafting content of 20 phr reduced to 3.3±1.2 µm, compared to that of neat UFPNR of 5.3±2.3 µm which also showed partial particle aggregation. It is also found that the impact strength of the filled PLA was enhanced to 33.4±5.6 kJ/m2 at PLA/UFPNR-gPMMA 20 wt% compared to neat PLA of 9.6±3 kJ/m2. The thermal degradation temperature of the PLA composites was enhanced with increasing UFPNR-g-PMMA content without affecting the glass transition temperature of the composites. The fracture surface of PLA/ UFPNR-g-PMMA suggested internal cavitation and crazes are the main effects of rubber toughening PLA with substantial interfacial interaction between the filler and the matrix.

Keywords: natural rubber, ultrafine fully vulcanized powder rubber, polylactic acid, polymer composites

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Authors: Mariam Badmus, Bothina Manasreh

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Transition metal dichalcogenides (TMDs) have gained significant attention as two-dimensional (2D) materials due to their intrinsic band gaps and unique properties, which make them ideal candidates for electronic and photonic applications. Unlike graphene, which lacks a band gap, TMDs (MX₂, where M is a transition metal and X is a chalcogen such as sulfur, selenium, or tellurium) exhibit semiconductor behavior and can be exfoliated into monolayers, enhancing their properties. The properties of these materials are investigated using density functional theory, a quantum mechanical computational method to solve Schrodinger equation for many body problems to calculate electron density of the atoms involved on which the energy and properties of a system depend. They show promise for use in photodetectors, biosensors, memory devices, and other technologies in communications, health, and energy sectors. In particular, metallic TMDs, which lack an intrinsic band gap, benefit from doping with transition metals, this improves their electronic and optical properties. Doping monolayer TMDs yields more significant improvements than doping bulk materials. Notably, doping with metals such as vanadium enhances the magnetization of TMDs, expanding their potential applications in spintronics. This work highlights the effects of doping on TMDs and explores strategies for optimizing their performance for advanced technological applications.

Keywords: concentration, doping, magnetization, monolayer

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Authors: Abdalla Ahmad Obeidat

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Developing efficient hydrogen storage materials is critical to advancing clean energy technologies, particularly for applications in fuel cells and renewable energy systems. This study explores materials for hydrogen storage through Density Functional Theory (DFT) calculations, addressing one of the most significant challenges in sustainable energy: the safe and efficient storage and release of hydrogen. Our research provides an in-depth analysis of various candidate compounds' structural and electronic properties, aiming to identify materials with enhanced hydrogen storage capacities. By investigating adsorption mechanisms and optimizing key material properties, we aim to contribute to developing high-performance hydrogen storage solutions. The findings from this work have the potential to impact the field of hydrogen fuel technology significantly, offering insights and advancements that support the transition to sustainable energy systems.

Keywords: hydrogen storage, density functional theory, electronic, thermal stability

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Authors: Henrique Gomes dos Santos, Manoel Henrique Alves, Jane Zoppas Ferreira, Annelise Kopp Alves

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This work aimed to seek an environmentally sustainable surface coating alternative by researching the influence of the addition of graphene oxide (GO) and carbon nanotubes (CNT) on the silanization of coatings to increase the wear resistance in galvanized steel, using the pin-on-disk test. The results obtained were compared between different concentrations of additives and the number of coating layers, in addition to comparing with samples without coating and only with silane layers. Bis-1,2-(triethoxysilyl)ethane (BTSE) silane was used in silanizing the coatings with CNT or GO and applied to the samples through dip-coating to form one, four, or eight layers. The wear test results found that three samples stood out in relation to the objective, showing an increase in wear resistance compared to the galvanized sample only. The rolling effect and the lubricity character presented by carbon nanotubes were positive for the increase in wear resistance obtained. The reduction in wear compared to the galvanized-only sample reached 82%. Raman spectroscopy was also carried out to detect the presence of silane, GO, and CNT, in addition to roughness tests and SEM to assess the homogeneity of the coating. The carbonaceous additives, graphene oxide, and carbon nanotubes in certain amounts of layers and specific concentrations fulfilled their objective against the wear imposed on the substrate.

Keywords: silane, coating, graphene oxide, carbon nanotubes, wear resistance

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Authors: F. Amor, A. Bouregba, N. El Fami, A. Diouri

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This study provides insights into the role of alkalis in modifying the hydration kinetics and microstructural development of β-dicalcium silicate, highlighting potential pathways for enhancing the performance of belite-based cements in various construction applications. It investigates the behavior of β-dicalcium silicates (β-Ca₂SiO₄) when hydrated in various alkaline environments, including deionized water and solutions containing 2M concentrations of Na₂CO₃, NaOH, KOH, and water glass. The dicalcium silicate was synthesized with laboratory reagents, calcium carbonate, and gel silica. The hydration process was carried out over different periods, ranging from 7 to 90 days. The hydrated samples were characterized using X-ray diffraction, infrared spectroscopy, and scanning electron microscopy, while the mechanical strength tests were performed at 28 and 90 days. The results indicate that the presence of alkalis significantly influences the hydration of belite cement. Early hydration is accelerated, which is evident from the faster dissolution of C₂S, a decrease in C₂S peaks, and the formation of C-S-H products, including sodium-containing C-(N)-S-H and potassium-containing C-(K)-S-H.

Keywords: dicalcium silicate, alkali activator, hydration, water glass, Na₂CO₃, NaOH, KOH

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Authors: Thian Khoon Tan, Poi Sim Khiew, Wee Siong Chiu, Chin Hua Chia

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This study investigates the efficacy of magnetically enhanced zinc oxide (MZnO) nanoparticles as a photocatalyst in the photodegradation of synthetic dyes, especially azo dyes. This magnetised zinc oxide has been simply fabricated by mechanical mixing through low-temperature calcination. This MZnO has been analysed through several analytical measurements, including FESEM, XRD, BET, EDX, and TEM, as well as VSM analysis which reflects successful fabrication. A high volume of azo dyes was found in industries effluent wastewater. They contribute to serious environmental stability and are very harmful to human health due to their high stability and carcinogenic properties. Therefore, five azo dyes, Reactive Red 120 (RR120), Disperse Blue 15 (DB15), Acid Brown 14 (AB14), Orange G (OG), and Acid Orange 7 (AO7), have been randomly selected to study their photodegradation property with reference to few characteristics, such as number of azo functional groups, benzene groups, molecular mass, and absorbance. The photocatalytic degradation efficiency was analysed by using a UV-vis spectrophotometer, where the reaction rate constant was obtained. It was found that azo dyes were significantly degraded through the first-order rate constant, which shows a higher kinetic constant as the number of azo functional groups and benzene group increases. However, the kinetic constant is inversely proportional to the molecular weight of these azo dyes.

Keywords: nanoparticles, photocatalyst, magnetically enhanced, wastewater, synthetic dyes, azo dyes

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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

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Authors: Karolina Kowalczyk-Skoczylas

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The hybrid SPD process called DRECE (Dual Rolls Equal Channel Extrusion) combines the concepts of ECAP method and CONFORM extrusion, and is intended for processing sheet-metal workpieces. The material in the fоrm оf a metal strip is subjected tо plastic defоrmation by passing thrоugh the shaping tоol at a given angle α. Importantly, in this process the dimensions of the metal strip dо nоt change after the pass is cоmpleted. Subsequent DRECE passes allоw fоr increasing the effective strain in the tested material. The methоd has a significant effect оn the micrоstructure and mechanical prоperties оf the strip. The experimental tests have been conducted on the unconventional DRECE device in VŠB Ostrava, the Czech Republic. The DC03 steel strips have been processed in several passes - up to six. Then, both Erichsen cupping tests as well as static tensile tests have been performed to evaluate the effect of DRECE process on drawability, plastic anisotropy and mechanical properties of the investigated steel. Both yield strength and ultimate tensile strength increase significantly after consecutive passes. Drawability decreases slightly after the first and second pass. Then it stabilizes on a reasonably high level, which means that the steel is characterized by useful drawability for technological processes. It was investigated in the material is characterized by a normal anisotropy. In the microstructure, an intensification of the development of microshear bands and their mutual intersection is observed, which leads to the fragmentation of the grain into smaller volumes and, consequently, to the formation of an ultrafine grained structure. "The project was co-financed by the European Union within the programme "The European Funds for Śląsk (Silesia) 2021-2027".

Keywords: SPD process, low carbon steel, mechanical properties, plastic deformation, microstructure evolution

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Authors: Gebregziabher Brhane Berhe, Wei-Nien Su, Bing Joe Hwang

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A new lithium-ion battery is configured by coupling sulfurized carbon anode and high voltage LiNi₀.₅Mn₁.₅O₄ (LNMO) cathode. The anode is derived from sulfurized polyacrylonitrile (S-C(PAN)). Severe capacity fading usually becomes unavoidable due to the oxidative decomposition of solvents, primarily when a conventional carbonate electrolyte with 1 M lithium hexafluorophosphate (LiPF6) is employed. Fluoroethylene carbonate (FEC), ethyl methyl carbonate (EMC), and 1, 1, 2, 2-Tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropyl ether (TTE) are formulated as the best electrolyte (3:2:5 in vol. ratio) for this new high-voltage lithium-ion battery to mitigate this capacity fading and improve the adaptability of the S-C(PAN) and LNMO. The discharge capacity of a full cell made with 1 M lithium hexafluorophosphate (LiPF6) in FEC/EMC/TTE (3:2:5) electrolyte reaches 688 mAh g⁻¹ at a rate of 2 C, while 19 mAh g⁻¹ for the control electrolyte. X-ray photoelectron spectroscopy (XPS) results confirm that the fluorinated electrolyte effectively stabilizes both surfaces of S-C(PAN) and LNMO in the full cell. Compared to the control electrolyte, the developed electrolyte enhances the cyclic stability and rate capability of both half cells (Li//S-C(PAN and Li//LiNi₀.₅Mn₁.₅O₄) and S-C(PAN)//LiNi₀.₅Mn₁.₅O₄ full cells.

Keywords: fluorinated electrolyte, high voltage, lithium-ion battery, polyacrylonitrile

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Authors: Aziz Ghoufi, Ayman Kanaan

Abstract:

Clean water is ubiquitous from drinking to agriculture and from energy supply to industrial manufacturing. Since the conventional water sources are becoming increasingly rare, the development of new technologies for water supply is crucial to address the world’s clean water needs in the 21st century. Desalination is in many regards the most promising approach to long-term water supply since it potentially delivers an unlimited source of fresh water. Seawater desalination using reverse osmosis (RO) membranes has become over the past decade a standard approach to produce fresh water. While this technology has proven to be efficient, it remains however relatively costly in terms of energy input due to the use of high-pressure pumps resulting of the low water permeation through polymeric RO membranes. Recently, water channels incorporated in lipidic and polymeric membranes were demonstrated to provide a selective water translocation that enables to break permeability- selectivity trade-off. Biomimetic Artificial Water channels (AWCs) are becoming highly attractive systems to achieve a selective transport of water. The first developed AWCs formed from imidazole quartet (I-quartet) embedded in lipidic membranes exhibited an ion selectivity higher than AQPs however associated with a lower water flow performance. Recently it has been conducted pioneer work in this field with the fabrication of the first AWC@Polyamide(PA) composite membrane with outstanding desalination performance. However, the microscopic desalination mechanism in play is still unknown and its understanding represents the shortest way for a long-term conception and design of AWC@PA composite membranes with better performance. In this work we gain an unprecedented fundamental understanding and rationalization of the nanostructuration of the AWC@PA membranes and the microscopic mechanism at the origin of their water transport performance from advanced molecular simulations. Using osmotic molecular dynamics simulations and a non-equilibrium method with water slab control, we demonstrate an increase in porosity near the AWC@PA interfaces, enhancing water transport without compromising the rejection rate. Indeed, the water transport pathways exhibit a single-file structure connected by hydrogen bonds. Finally, by comparing AWC@PA and PA membranes, we show that the difference in water flux aligns well with experimental results, validating the model used.

Keywords: water desalination, biomimetic membranes, molecular simulation, nanochannels

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Authors: Sirine Sayed, Mahrez Ait Mohammed, Mourad Nachtane, Abdelwahed Barkaoui, Khalid Bouziane, Mostapha Tarfaoui

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This study addresses a critical challenge in transitioning to a hydrogen-based economy by introducing and validating a one-dimensional (1D) tool for modelling hydrogen permeability through hybrid materials, focusing on tank applications. The model developed integrates rigorous experimental validation, published data, and advanced computational modelling using the PanDiffusion framework, significantly enhancing its validity and applicability. By elucidating complex interactions between material properties, storage system configurations, and operational parameters, the tool demonstrates its capability to optimize design and operational parameters in real-world scenarios, as illustrated through a case study of hydrogen leakage. This comprehensive approach to assessing hydrogen permeability contributes significantly to overcoming key barriers in hydrogen infrastructure development, potentially accelerating the widespread adoption of hydrogen technology across various industrial sectors and marking a crucial step towards a more sustainable energy future.

Keywords: hydrogen storage, composite tank, permeability modelling, PanDiffusion, energy carrier, transportation technology

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Authors: A. Bouhmouche, I. Rhrissi, A. Jabar, R. Moubah

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Quantum spin liquids (QSLs), known for their competing interactions that prevent conventional ordering, exhibit emergent phenomena and exotic properties resulting from quantum correlations. Despite these recent advancements in QSLs, a significant portion of the optical and thermodynamic properties in the Kagome lattice remains unknown. In addition, the thermodynamic phenomenology of NaRuO₂ bears a resemblance to that of highly frustrated magnets. Here, we employed ab-initio calculations to explore the electronic, optical and thermodynamic properties of NaRuO₂, a new QSL candidate. NaRuO₂ was identified as a semiconductor with a small bandgap energy of 0.69 eV. Our results reveal huge anisotropic optical properties, in which a distinct refractive index within the ab-plane indicating an impressive birefringent character of the NaRuO₂ system and a significant enhancement of the optical absorption coefficient and optical conductivity in the in-plane with respect to the c-axis. The investigation also examines the electronic anisotropy of the gap energy; by applying strain, the gap energy displays significant variations in the ab-plane compared to the out-of-plane direction. Conversely, calculations of the thermodynamic properties reveal a low thermal conductivity (2.5-0.5 W.m-¹. K-¹) and specific heat, which suggests the existence of strong interactions among the NaRuO₂ quantum spins. The linear specific heat behavior observed in NaRuO₂ suggests the fractionalization of electrons and the presence of a spinons Fermi surface. These findings hold promising potential for future quantum applications.

Keywords: quantum spin liquids, anisotropy, hybrid-DFT, applied strain, optoelectronic and thermodynamic properties

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Authors: Ibrahim Dauda Muhammad, Mokhtar Awang

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To synthesize a specific phase of zirconia (ZrO₂) nanotubes, zirconium (Zr) foil was subjected to the anodization process in a fluorine-containing electrochemical bath for a fixed duration. The resulting zirconia nanotubes (ZNTs) were then characterized using various techniques, including UV-vis spectroscopy, Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD). The XRD diffraction pattern confirmed that the ZNTs were crystalline, with a predominant texture along the [111] direction, indicating that the majority of the phase was cubic. TEM images revealed that most of the nanotubes were vertically aligned and self-organized, with diameters ranging from 32.9 to 38.8 nm and wall thicknesses between 3.0 and 7.3 nm. Additionally, the synthesized ZNTs had a length-to-width ratio of 235, which closely matches the ratio of 240 observed in another study where anodization was not used. This study demonstrates that a specific phase of zirconia nanotube can be successfully synthesized, with promising potential applications in catalysis and other areas.

Keywords: zirconia nanotubes, anodization, characterization, cubic phase

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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

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Authors: Cristian Rodriguez, Jose M. Davila, Aguasanta M. Sarmiento, María L. de la Torre

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There are many acidic environments that degrade structural concrete, such as those found in water treatment plants, sports facilities, and more, but one of the most aggressive is undoubtedly the water from acid mine drainage. This phenomenon occurs in all pyrite mining facilities and, to a lesser extent, in coal mines and is characterised by very low pH values and high sulphate, metal, and metalloid contents. This phenomenon causes significant damage to the concrete, mainly attacking the binder. In addition, the process is accentuated by the action of acidophilic bacteria, which accelerate the cracking of the concrete. Due to the damage that concrete experiences in acidic environments, the authors of this study aimed to enhance its performance in various aspects. Thus, two solutions have been proposed to improve the concrete durability, acting both on the mass of the material itself with the incorporation of fibres, and on its surface, proposing treatments with two different paints. The incorporation of polypropylene fibres in the concrete mass aims to improve the tensile strength of concrete, being this parameter the most affected in this type of degradation. The protection of the concrete with surface paint is intended to improve the performance against abrasion while reducing the access of water to the interior of the mass of the material. Sulpho-resistant cement has been used in all the mass concrete mixtures that have been prepared, in addition to complying with the requirements of the current Spanish standard, equivalent to the Eurocodes. For the polypropylene fibres, two alternatives have been used, with 1.7 and 3.4 kg/m³, while as surface treatment, the use of two paints has been analysed, one based on polyurethane and the other on asphalt-type paint. The proposed treatments have been analysed by means of indirect tensile tests and pressure sandblasting, thus analysing the effects of abrasion. The results obtained have confirmed a slight increase in the tensile strength of mass concrete by incorporating polypropylene fibres, being slightly higher for a ratio of 3.4 kg/m³, with an improvement of slightly more than 5% in the tensile strength of concrete. However, the use of fibres in concrete greatly reduces the loss of concrete mass due to abrasion. This improvement against abrasion is even more significant when paint is used as an external protection measure, with a much lower loss of mass with both paints. Acknowledgments: This work has been supported by MICIU/AEI/10.13039/501100011033/FEDER, UE, throughout the project PID2021-123130OB-I00.

Keywords: degradation, concrete, tensile strength, abrasion

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Authors: Mehmet Ucar, Nuray Ucar

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Both thermal insulation and sound insulation play a key role in energy saving and the quality of life. In this study, the effects of different fillers, such as silica aerogel and polystyrene, on the tensile strength, thermal insulation, and sound insulation of epoxy composites have been analyzed. Results from the experimental studies show that both tensile strength and insulation properties (sound and thermal insulation) of the epoxy composite increased by the use of silica aerogel additive. Polystyrene additive significantly increases the sound absorption coefficient of the epoxy composite. Such composites offer great potential for many applications.

Keywords: epoxy composite, silica aerogel, polystyrene, tensile strength, thermal insulation, sound insulation

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Authors: Maria Luisa de la Torre, Javier Aroba, Jose Miguel Davila, Aguasanta M. Sarmiento

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Steel is one of the most widely used materials in polymetallic sulfide mining installations. One of the main problems suffered by these facilities is the economic losses due to the corrosion of this material, which is accelerated and aggravated by the contact with acid waters generated in these mines when sulfides come into contact with oxygen and water. This generation of acidic water, in turn, is accelerated by the presence of acidophilic bacteria. In order to gain a more detailed understanding of this corrosion process and the interaction between steel and acidic water, a laboratory experiment was carried out in which carbon steel plates were introduced into four different solutions for 27 days: distilled water (BK), which tried to assimilate the effect produced by rain on this material, an acid solution from a mine with a high Fe2+/Fe3+ (PO) content, another acid solution of water from another mine with a high Fe3+/Fe2+ (PH) content and, finally, one that reproduced the acid mine water with a high Fe2+/Fe3+ content but in which there were no bacteria (ST). Every 24 hours, physicochemical parameters were measured and water samples were taken to carry out an analysis of the dissolved elements. The results of these measurements were processed using an explainable AI model based on fuzzy logic. It could be seen that, in all cases, there was an increase in pH, as well as in the concentrations of Fe and, in particular, Fe(II), as a consequence of the oxidation of the steel plates. Proportionally, the increase in Fe concentration was higher in PO and ST than in PH because Fe precipitates were produced in the latter. The rise of Fe(II) was proportionally much higher in PH and, especially in the first hours of exposure, because it started from a lower initial concentration of this ion. Although to a lesser extent than in PH, the greater increase in Fe(II) also occurred faster in PO than in ST, a consequence of the action of the catalytic bacteria. On the other hand, Cu concentrations decreased throughout the experiment (with the exception of distilled water, which initially had no Cu, as a result of an electrochemical process that generates a precipitation of Cu together with Fe hydroxides. This decrease is lower in PH because the high total acidity keeps it in solution for a longer time. With the application of an artificial intelligence tool, it has been possible to evaluate the effects of steel corrosion in mining environments, corroborating and extending what was obtained by means of classical statistics. Acknowledgments: This work has been supported by MCIU/AEI/10.13039/501100011033/FEDER, UE, throughout the project PID2021-123130OB-I00.

Keywords: carbon steel, corrosion, acid mine drainage, artificial intelligence, fuzzy logic

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Authors: Yodai Ashikubo, Toshiaki Suzuki, Satoshi Kouya, Mitsuya Motohashi

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Functional microstructures such as wires, fins, needles, and rolls are currently being applied to variety of high-performance devices. Under these conditions, a roll structure (silicon micro-nanoroll) was formed on the surface of the silicon substrate via fine bubbles during anodization using an extremely diluted hydrofluoric acid (HF + H₂O). The as-formed roll had a microscale length and width of approximately 1 µm. The number of rolls was 3-10 times and the thickness of the film forming the rolls was about 10 nm. Thus, it is promising for applications as a distinct device material. These rolls functioned as capsules and/or pipelines. To date, number of rolls and roll length have been controlled by anodization conditions. In general, controlling the position and roll winding state is required for device applications. However, it has not been discussed. Grooves formed on silicon surface before anodization might be useful control the bubbles. In this study, we investigated the effect of the grooves on the position and shape of the roll. The surfaces of the silicon wafers were anodized. The starting material was p-type (100) single-crystalline silicon wafers. The resistivity of the wafer is 5-20 ∙ cm. Grooves were formed on the surface of the substrate before anodization using sandpaper and diamond pen. The average width and depth of the grooves were approximately 1 µm and 0.1 µm, respectively. The HF concentration {HF/ (HF + C₂H5OH + H₂O)} was 0.001 % by volume. The C2H5OH concentration {C₂H5OH/ (HF + C₂H5OH + H₂O)} was 70 %. A vertical single-tank cell and Pt cathode were used for anodization. The silicon roll was observed by field-emission scanning electron microscopy (FE-SEM; JSM-7100, JEOL). The atomic bonding state of the rolls was evaluated using X-ray photoelectron spectroscopy (XPS; ESCA-3400, Shimadzu). For straight groove, the rolls were formed along the groove. This indicates that the orientation of the rolls can be controlled by the grooves. For lattice-like groove, the rolls formed inside the lattice and along the long sides. In other words, the aspect ratio of the lattice is very important for the roll formation. In addition, many rolls were formed and winding states were not uniform when the lattice size is too large. On the other hand, no rolls were formed for small lattice. These results indicate that there is the optimal size of lattice for roll formation. In the future, we are planning on formation of rolls using groove formed by lithography technique instead of sandpaper and the pen. Furthermore, the rolls included nanoparticles will be formed for nanodevices.

Keywords: silicon roll, anodization, fine bubble, microstructure

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Authors: Aguasanta Miguel Sarmiento, José Miguel Dávila, María Luisa de la Torre

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Acid mine drainage (AMD) is an acidic leachate with high levels of metals and sulphates in solution, which seriously affects the durability and strength of metallic materials used in the construction of structural and mechanical components. This paper presents the results of the evolution over time of the reduction in tensile strength and defects in AISI 304 stainless steel in contact with acid mine drainage. For this purpose, a total of 30 bars with a diameter of 8 mm and a length of 14 cm were placed transversely in the course of a stream contaminated by AMD from the sulphide mines of the Iberian Pyritic Belt (SW Spain). This stream has average pH values of 2.6, a potential of 660 mV, and average concentrations of 12 g/L of sulphates, 1.2 g/L of Fe, 191 mg/L of Zn, etc. Every two months of exposure, 6 stainless steel bars were extracted from the acid stream. They were subjected to surface roughness analysis carried out with the help of Mitutoyo Surftest SJ-210 surface roughness tester. The analysis was carried out at three different points on 5 specimens from each series. The average reading of each parameter is calculated in order to ensure the accuracy of the measurements and the surface coverage. Arithmetic mean roughness value (Ra), mean roughness depth (Rz), and root mean square roughness (Rq) were measured. Five specimens from each series were statically tensile tested using universal equipment (Servosis ME 403 of 200kN). The specimens were clamped at their ends with two grips for cylindrical sections, and the tensile force was applied at a constant speed of 0.5 kN/s, according to the requirements of standard UNE-EN ISO 6892-1: 2020. To determine the modulus of elasticity, limits close to 15% and 55% of the maximum load were used, depending on the course of each test. Field Emission Scanning Electron Microscopy (FESEM) was used to observe corrosion products and defects generated by exposure to AMD. Energy dispersive X-ray spectrometry (EDS) was used to analyse the chemical composition of the corrosion products formed. For this purpose, small pieces were cut from the resulting specimens, cleaned, and embedded in epoxy resin. The results show that after only 5 months of exposure of AISI 304 stainless steel to the mining environment, the surface roughness increases significantly, with average depths almost 6 times greater than the initial one. Cracks are observed on the surface of the material, which increases in size with the time of exposure. A large number of grains with a composition of more than 57% Pb and 16% Sn can be observed inside these cracks. Tensile tests show a reduction in the resistance of this material after only two months of exposure. The results show the serious problems that would result from the use of this material for the use of mechanical components in a sulphide mining environment, not only because of the significant reduction in the lifetime of such components, but also because of the implications for human safety.

Keywords: acid mine drainage, corrosion, mechanical properties, stainless steel

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Authors: Jean-Francois Feller

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The analysis of the volatolome emitted by the human body with a sensor array (e-nose) is a method for clinical applications full of promises to make an olfactive fingerprint characteristic of people's health state. But the amount of volatile organic compounds (VOC) to detect, being in the range of parts per billion (ppb), and their diversity (several hundred) justifies developing ever more sensitive and selective vapor sensors to improve the discrimination ability of the e-nose, is still of interest. Quantum resistive vapour sensors (vQRS) made with nanostructured conductive polymer nanocomposite transducers have shown a great versatility in both their fabrication and operation to detect volatiles of interest such as cancer biomarkers. However, it has been shown that their chemo-resistive response was highly dependent on the quality of the inter-particular junctions in the percolated architecture. The present work investigates the effectiveness of poly(hedral oligomeric silsesquioxane) acting as a nanospacer to amplify the disconnectability of the conducting network and thus maximize the vQRS's sensitivity to VOC.

Keywords: volatolome, quantum resistive vapour sensor, nanostructured conductive polymer nanocomposites, olfactive diagnosis

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Authors: Riya Thomas, Denis Music, Tautgirdas Ruzgas

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The detection of tyrosinase holds considerable interest in the domains of food nutrition and human health due to its significant role in causing a detrimental effect on the colour, flavour, and nutritional value of food as well as in the synthesis of melanin causing skin melanoma. Compared to other conventional analytical techniques, electrochemical (EC) sensors are highly promising owing to their quick response, great sensitivity, ease of use, and low cost. Particularly, titania nanoparticle-based electrochemical sensors have drawn special attention in identifying several biomolecules including enzymes, antibodies, and receptors, owing to their enhanced electrocatalytic activity and electron-accepting properties. In this study, Ti-O film-modified electrode is fabricated using reactive magnetron sputtering, and its affinity towards tyrosinase is examined via electrochemical methods. To comprehend the physiochemical and surface properties-governed electrocatalytic activity of modified electrodes, Ti-O films are grown under various compositional ranges and deposition temperature, and their corresponding electrochemical activity towards tyrosinase is studied. Further, to understand the underlying atomistic mechanisms and electronic-scale electrochemical characteristics, density functional theory (DFT) is employed. The main goal of the current work is to determine the correlation between macroscopic measurements and the underlying atomic properties to improve the tyrosinase activity on Ti-O surfaces. Moreover, this work offers an intriguing new perspective on the use of Ti-O-modified electrodes to detect tyrosinase in the areas of clinical diagnosis, skincare, and food science.

Keywords: density functional theory, electrochemical sensor, Ti-O film, tyrosinase

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Authors: A. Kaibi, A. Guittoum, M. Hemmous, D. Martínez-Blanco, P. Gorria, J. A. Blanco, M. Kechouane

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The present work deals with the effect of Si content on the physical properties of nanostructured (Ni75Fe25)100-x Six (x=0, 3.5, 6.5, 9, 12, and 15 at %) powders elaborated by mechanical alloying for a milling time of 96 h. The microstructure, hyperfine, and magnetic properties of the powders were investigated as a function of Si content by means of X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Mössbauer Spectroscopy, and Vibrating Sample magnetometry (VSM). From XRD spectra, the formation of FCC disordered Ni (Fe,Si) solid solution was evidenced after 96 h. As Si content increases, the lattice parameter and the grain size decrease (from ~28 to 15 nm), while the microstrain level decreases from 0.98% to 0.65%. From SEM micrographs, we showed that powder particles become round in shape and decrease in size with increasing Si content. For all Si content, the adjustment of Mössbauer spectra confirmed the formation of a disordered ferromagnetic NiFeSi phase. From hysteresis curves, we have extracted the values of saturation magnetization and coercive field for all powders. The evolution of Ms and Hc as a function of Si content will be discussed.

Keywords: nanostructured powders, (Ni75Fe25)100-xSix alloy, microstructure, magnetic properties

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Authors: Johannes Keil, Eric Mischorr, Veit Würfel, Jan Condé-Wolter, Alexander Liebsch, Maik Gude

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In the aviation sector wastewater pipes are subjected to many different mechanical and medial loads. Worst-case scenarios include high-velocity impacts resulting from the introduction of foreign objects into the system. The industry is seeking to reduce the weight of these pipes, which are currently manufactured from titanium. A promising alternative is the use of fiber-reinforced polymers (FRP), specifically carbon fiber (CF) reinforced polyaryletherketone (PAEK) laminates. This study employs an experimental methodology to investigate the impact resistance of CF/PAEK laminates, with a particular focus on three configurations: crimp, non-crimp, and interleaved matrix rich films in cross-ply laminates. High-velocity impacts were performed using a gas gun resulting in three-dimensional damage patterns. Afterwards the damage behavior was qualitatively and quantitatively analyzed using ultrasonic scans and computed tomography (CT). Samples with an interleaved matrix-rich film led to a reduction of the damage area by around 40% compared to the non-interleaved, non-crimp samples, while the crimp architecture resulted in a reduction of more than 60%. Therefore, these findings contribute to understanding the influence of laminate architecture on impact resistance, paving the way for more efficient materials in aviation applications.

Keywords: fracture toughness, high-velocity-impact, textile architecture, thermoplastic composites

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