ME - Artigos em revistas internacionais
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- Thermal Stability and Irradiation Resistance of (CrFeTiTa)70W30 and VFeTiTaW High Entropy AlloysPublication . Pereira, André; Martins, Ricardo; Monteiro, Bernardo; Correia, Jose B.; Galatanu, Andrei; Catarino, Norberto; Jenus, Petra; Dias, MartaABSTRACT: Nuclear fusion is a promising energy source. The International Thermonuclear Experimental Reactor aims to study the feasibility of tokamak-type reactors and test technologies and materials for commercial use. One major challenge is developing materials for the reactor's divertor, which supports high thermal flux. Tungsten was chosen as the plasma-facing material, while a CuCrZr alloy will be used in the cooling pipes. However, the gradient between the working temperatures of these materials requires the use of a thermal barrier interlayer between them. To this end, refractory high-entropy (CrFeTiTa)70W30 and VFeTiTaW alloys were prepared by mechanical alloying and sintering, and their thermal and irradiation resistance was evaluated. Both alloys showed phase growth after annealing at 1100 degrees C for 8 days, being more pronounced for higher temperatures (1300 degrees C and 1500 degrees C). The VFeTiTaW alloy presented greater phase growth, suggesting lower microstructural stability, however, no new phases were formed. Both (as-sintered) alloys were irradiated with Ar+ (150 keV) with a fluence of 2.4 x 1020 at/m2, as well as He+ (10 keV) and D+ (5 keV) both with a fluence of 5 x 1021 at/m2. The morphology of the surface of both samples was analyzed before and after irradiation showing no severe morphologic changes, indicating high irradiation resistance. Additionally, the VFeTiTaW alloy presented a lower deuterium retention (8.58%) when compared to (CrFeTiTa)70W30 alloy (14.41%).
- Tetrahedrite Nanocomposites for High Performance ThermoelectricsPublication . Coelho, Rodrigo; Moço, Duarte; Sá, Ana; Luz, Paulo P. da; Neves, Filipe; Cerqueira, Maria de Fátima; Lopes, E.B.; Brito, Francisco; Mangelis, Panagiotis; Kyratsi, Theodora; Pereira Gonçalves, AntonioABSTRACT: Thermoelectric (TE) materials offer a promising solution to reduce green gas emissions, decrease energy consumption, and improve energy management due to their ability to directly convert heat into electricity and vice versa. Despite their potential, integrating new TE materials into bulk TE devices remains a challenge. To change this paradigm, the preparation of highly efficient tetrahedrite nanocomposites is proposed. Tetrahedrites were first prepared by solid state reaction, followed by the addition of MoS2 nanoparticles (NPs) and hot-pressing at 848 K with 56 MPa for a duration of 90 min to obtain nanocomposites. The materials were characterized by XRD, SEM-EDS, and Raman spectroscopy to evaluate the composites' matrix and NP distribution. To complement the results, lattice thermal conductivity and the weighted mobility were evaluated. The NPs' addition to the tetrahedrites resulted in an increase of 36% of the maximum figure of merit (zT) comparatively with the base material. This increase is explained by the reduction of the material's lattice thermal conductivity while maintaining its mobility. Such results highlight the potential of nanocomposites to contribute to the development of a new generation of TE devices based on more affordable and efficient materials.
- New proton exchange membranes based on ionic liquid doped chitosanPublication . Naffati, Naima; Teixeira, Fatima; Teixeira, António Paulo Silva; Rangel, Carmen M.ABSTRACT: The development of new proton exchange membranes (PEM) for electrochemical devices have attracted researcher's attention in the pursuit for more sustainable and cost-effective technologies for clean energy production and conversion. In this work, new doped chitosan (CS) membranes were prepared by the casting method. Chitosan is an abundant, biodegradable and non-toxic material, and as a membrane, a sustainable and cheaper alternative to those perfluorinated and commonly used, such as Nafion. Three different ionic liquids were employed as dopants, ([EMIM][OTf], [EMIM][FSI] and [MIMH][HSO4]), in various concentrations and up to 50 wt% load. The new membranes were characterized by ATR-FTIR, thermogravimetry, using TGA and DSC techniques to assess their thermal properties, and by SEM, to analyse their surface morphology. Proton conduction properties of the new membranes were assessed by Electrochemical Impedance Spectroscopy (EIS). The new doped membranes showed an increase in the proton conduction compared with pristine chitosan membranes. The incorporation of ionic liquids into chitosan membranes improved their proton conductivity and thermal properties, with [EMIM][OTf] and [MIMH][HSO4] showing the most promising results. A 2-fold increment in the proton conduction was generally observed with the increase of the temperature from 30 to 60 degrees C. The best proton conductivity was found at 60 degrees C for the membrane doped with [EMIM][OTf], with a value of 47 mS.cm(-1).
- Thermally modified wood: assessing the impact of weathering on mechanical strength and exposure to subterranean termitesPublication . Godinho, Delfina; Lourenco, Ana; Araújo, Solange; Machado, José Saporiti; Nunes, Lina; Duarte, Marta; Duarte, Sónia; Ferreira, Cristina; Quilhó, Teresa; Cunha Diamantino, Teresa; Gominho, JorgeABSTRACT: The main objective of this study was to evaluate the mechanical properties of three thermal-modified wood species when exposed to weathering in urban and maritime/industrial environments and their durability against subterranean termites. The wood species studied were Maritime pine, ash, and blackwood acacia. All wood samples were exposed to two different environments (urban and maritime/industrial) for 24 months. Then, its physical and mechanical properties were evaluated (modulus of elasticity (MOE), modulus of rupture (MOR), compression strength (CS), and modulus of compression (MOC). Thermally modified woods revealed a lower density, which could explain the loss of MOE and MOR. In compression, no significant changes were verified. The weathered samples showed changes in mechanical properties, mostly verified in MOE and MOR, where some decreases were reported in both locations. Tests were performed to evaluate biodegradation and the resistance of all wood samples to subterranean termites. The grade of attack (approximate to 4) and termite survival rate were similar in all wood species (above 75% and lower than 80%), except for modified acacia (59%), which could indicate that thermal modification increased toxic substances. The cellulose degradation was reflected in FTIR-ATR and Py-GC/MS in natural and thermally modified woods. Py-GC/MS showed a decrease in levoglucosan, while lignin suffered some modifications with slight changes in monomeric composition reflected by the reduction of the S/G ratio. No changes were found between the two environments, and thermal modification did not give extra protection against termites and weathering.
- Thermoelectric Properties of Tetrahedrites Produced from Mixtures of Natural and Synthetic MaterialsPublication . Santos, Beatriz; Esperto, Luís; Figueira Vasques, Isabel; Mascarenhas, João; Lopes, E.B.; Salgueiro, Rute; Silva, Teresa; Correia, Jose B.; de Oliveira, Daniel Pipa Soares; Pereira Gonçalves, Antonio; Neves, FilipeABSTRACT: Thermoelectric materials have considerable potential in the mitigation of the global energy crisis, through their ability to convert heat into electricity. This study aims to valorize natural resources, and potentially reduce production costs, by incorporating tetrahedrite-tennantite (td) ores from the Portuguese Iberian Pyrite Belt into synthetic samples. The ore samples were collected in a mine waste at Barrig & atilde;o and as "dirty-copper" pockets of ore from the Neves Corvo mine. Subsequently, high-energy ball milling and hot pressing were employed in the production of thermoelectric materials. These are characterized by XRD, SEM/EDS, and thermoelectrical properties. The complete dissolution of the dump material sulfides with the synthetic tetrahedrite constituents led to an increase in the amount of the tetrahedrite-tennantite phase, which was made up of a tetrahedrite-tennantite-(Fe) solid solution. The thermoelectric characterization of these materials is provided, revealing that most of the combined synthetic ore samples displayed better results than the pristine tetrahedrite, mostly due to higher Seebeck coefficient values. Furthermore, the best thermoelectric performance is achieved with 10% of ore, where a power factor of 268 mu W.K-2.m-1 is reached at room temperature.
- Exploring Marine Biomineralization on the Al-Mg Alloy as a Natural Process for In Situ LDH Growth to Improve Corrosion ResistancePublication . Marques, Maria João; Mercier, Dimitri; Seyeux, Antoine; Zanna, Sandrine; Tenailleau, Christophe; Duployer, Benjamin; Jeannin, Marc; Marcus, Philippe; Basséguy; BASSEGUY, RegineABSTRACT: This study provides a detailed characterization of the AA5083 aluminum alloy, surface, and interface over 6 months of immersion in seawater, employing techniques such as SEM/EDX, GIXRD, mu-Raman and XPS. The purpose was to evaluate the evolution of the biomineralization process that occurs on the Al-Mg alloy. By investigating the specific conditions that favor the in situ growth of layered double hydroxide (LDH) during seawater immersion as a result of biomineralization, this research provides insights into marine biomineralization, highlighting its potential as an innovative and sustainable strategy for corrosion protection.
- Evolution of atomically dispersed co-catalysts during solar or UV photocatalysis for efficient and sustained H2 productionPublication . Capelo, Anabela; Fattoruso, Domenico; Valencia-Valero, Laura; Esteves, M. Alexandra; Rangel, Carmen M.; Puga, AlbertoABSTRACT: The evolution of metal/titania photocatalysts during photocatalytic H-2 evolution is herein studied. Samples containing atomically dispersed Pt co-catalysts (single atoms, clusters and sub-nanoparticles) formed after calcination were compared to pre-reduced analogues mostly having metallic nanoparticles (diameters >1 nm) during ethanol photoreforming under either UV-rich irradiation or natural sunlight. Aggregation of ultra-dispersed oxidised platinum entities (Pt delta+) with concomitant reduction into Pt-0 nanoparticles (1-2 nm) was observed after UV irradiation by transmission electron microscopy (TEM), and diffuse reflectance UV-visible (DRUV-vis) and X-ray photoelectron (XPS) spectroscopies. A parallel, albeit slower, evolution trend was evidenced during solar photocatalysis. Conversely, atomically dispersed Cu co-catalyst species did not grow and became in-situ reduced into sub-nanometric Cu-0 under irradiation. Hydrogen production rates were remarkably high during initial stages of UV irradiation, and then declined to a sustained regime (approximate to 50 and 8 mmol g(-1) h(-1) for Pt/TiO2 or Cu/TiO2, respectively, for up to 24 h of irradiation). Steadier solar photoreforming was observed in experiments performed in a compound parabolic collector tubular reactor (approximate to 7.6 and 1.7 mmol g(-1) h(-1) for Pt/TiO2 or Cu/TiO2, respectively). Despite the non-negligible effect of co-catalyst rearrangement on activity rationalised herein, attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy measurements pre- and post-photocatalysis suggest that accumulation of strongly adsorbed degradation intermediates, chiefly acetate, is a major cause for rate decreases. Notwithstanding, this phenomenon did not result in total deactivation, so that sustained hydrogen production upon long-term irradiation was not compromised.
- Detection of corrosion on silvered glass reflectors via image processingPublication . Wiesinger, Florian; Baghouil, Sarah; Le Baron, Estelle; Collignon, Romain; Santos, Filipa; Cunha Diamantino, Teresa; Catarino, Isabel; Facão, Jorge; Ferreira, Cristina; Páscoa, Soraia; Sutter, Florian; Fernández-García, Aránzazu; Wette, JohannesABSTRACT: A novel characterization technique based on image analysis is presented, intended to complement state-of-the-art reflectometer measurements. The technique is developed by experts from different laboratories (OPAC, AGC, CEA and LNEG), which subsequently conduct two Round Robin experiments on corroded solar reflectors for validation. Regarding the inter-comparability, it is found that parameters like the corrosion spot density or the penetration maximum on coated edges exhibit an average coefficient of variation of 62.6 % and 54.9 %. Better agreement is found for parameters like the total corroded area and the maximum edge corrosion penetration, with coefficients of variation of 14.3 % and 13.4 %, respectively. The developed methodology is further applied during a 68-month lasting outdoor exposure campaign of two types of solar reflectors at two representative sites, one exhibiting corrosivity class C2 and the other C3. On the commercial coating RL1, a total corroded area of 59 mm2 and 426 mm2 is measured after the outdoor exposure on the C2 and the C3 site, respectively, while on the novel low-lead coated reflector RL3 corresponding values are 280 mm2 and 1308 mm2. This shows the superior quality of the coating RL1 in terms of corrosion resistance. Furthermore, the analysis highlights the importance of proper edge sealing for corrosion protection, since corrosion penetration is increased by a factor between 1.3 and 4.0 if the edges are unprotected. The reflectance decrease after the outdoor exposure is regarded as negligible (0.000 - 0.005), thus not permitting any of the conclusions that are made from the novel image analysis technique.
- Simulation of Surface Segregation in Nanoparticles of Pt-Pd AlloysPublication . Correia, Jose B.; Sá, AnaABSTRACT: Platinum (Pt) and palladium (Pd) are crucial in hydrogen energy technologies, especially in fuel cells, due to their high catalytic activity and chemical stability. Pt-Pd nanoparticles, produced through various methods, enhance catalytic performance based on their size, shape, and composition. These nanocatalysts excel in direct methanol fuel cells (DMFCs) and direct ethanol fuel cells (DEFCs) by promoting alcohol oxidation and reducing CO poisoning. Pt-Pd catalysts are also being explored for their oxygen reduction reaction (ORR) on the cathodic side of fuel cells, showing higher activity and stability than pure platinum. Molecular dynamics (MD) simulations have been conducted to understand the structural and surface energy effects of PdPt nanoparticles, revealing phase separation and chemical ordering, which are critical for optimizing these catalysts. Pd migration to the surface layer in Pt-Pd alloys minimizes the overall potential energy through the formation of Pd surface monolayers and Pt-Pd bonds, leading to a lower surface energy for intermediate compositions compared to that of the pure elements. The potential energy, calculated from MD simulations, increases with a decreasing particle size due to surface creation, indicating higher reactivity for smaller particles. A general contraction of the average distance to the nearest neighbour atoms was determined for the top surface layers within the nanoparticles. This research highlights the significant impact of Pd segregation on the structural and surface energy properties of Pt-Pd nanoparticles. The formation of Pd monolayers and the resulting core-shell structures influence the catalytic activity and stability of these nanoparticles, with smaller particles exhibiting higher surface energy and reactivity. These findings provide insights into the design and optimization of Pt-Pd nanocatalysts for various applications.
- Investigation of the Effect of Milling Time on Elemental Powders of Oxi-Reduction Nickel and Hydrogenation : Dehydrogenation TitaniumPublication . Teixeira, Rodolfo da Silva; Gurgel, Mônica Aline Magalhães; Rodrigues, Patricia Freitas; Freitas, Bruno Xavier de; Le Sénéchal, Naiara; Oliveira, R. V.; Neves, Filipe; Paula, Andersan dos SantosABSTRACT: Mechanical alloying (MA) is widely applied in the synthesis of blended elemental or prealloyed powders. This work evaluates the effect of milling time on elemental nickel and titanium powders produced by oxi-reduction and the hydrogenation-dehydrogenation process, respectively. The powders are characterized by scanning electron microscopy, X-ray diffraction, particle size, powder yield, and differential scanning calorimetry. It is observed that increasing the milling time promotes the formation of a structure composed of thin lamellae of nickel and titanium, which results in the beneficial effect of lowering the temperature for the formation of the intermetallic of the Ni-Ti system and in the powder yield achieved. The reduction of milling time in the MA process of NiTi alloys enhances technological efficiency by decreasing their overall processing time.