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  • Structural and Optical Characterization of Mechanochemically Synthesized CuSbS2† [Abstract]
    Publication . Esperto, Luís; Figueira, Isabel; Mascarenhas, João; Silva, Teresa; Correia, J.B.; Neves, Filipe
    ABSTRACT: The present work describes experimental studies related to the characterization of CuSbS2 directly synthesized after 2 h of mechanochemical synthesis (MCS) at 340 rpm, starting from mixtures of elemental powders. X-ray diffraction (XRD) and UV-VIS-NIR spectroscopy were carried out to analyze the crystal structure, degree of crystallinity, crystallite size and optical properties of the mechanochemically synthesized CuSbS2 powders. Rietveld refinement was carried out using Diffrac. TOPAS (Bruker AXS). Thermal stability of the synthesized materials was evaluated by the vacuum thermal heat treatment of the mechanochemically synthesized CuSbS2 powders at 350 °C for 24 h. Furthermore, the CuSbS2 powders were also analyzed by field-emission scanning electron microscopy (FE-SEM), laser diffraction, and differential thermal analysis.
  • Processamento de materiais termoelétricos baseados na tetraedrite usando minério de tetraedrite-tenantite
    Publication . Esperto, Luís; Figueira, Isabel; Mascarenhas, João; Salgueiro, Rute; Silva, Teresa; Lopes, E.B.; Gonçalves, António Pereira; Correia, J.B.; de Oliveira, Daniel Pipa Soares; Almeida, P.; Neves, Filipe
    RESUMO: O desenvolvimento e implementação de tecnologias com baixo potencial de aquecimento global e energeticamente eficientes requer uma contínua inovação na área dos materiais para a energia. Nesta estratégia insere-se a pesquisa sobre o processamento de materiais termoelétricos baseados na tetraedrite. No presente trabalho procede-se à avaliação da viabilidade da incorporação direta, sem qualquer pré-tratamento, de minério da série tetraedrite-tenantite no processamento de materiais à base de tetraedrite por síntese mecanoquímica. Para tal prepararam-se misturas de pós contendo diferentes rácios de amostras de tetraedrite sintética, também obtida por síntese mecanoquímica, e de amostras de minério, recolhidas na mina de Neves-Corvo e na escombreira da mina do Barrigão. A caraterização estrutural e microestrutural dos materiais processados após 1 h e 2 h de síntese mecanoquímica permitiu verificar a formação de um composto constituído por tetraedrite-tenantite-(Fe) como fase principal, independentemente do minério de origem. Estes resultados são uma indicação do sucesso da abordagem seguida.
  • Structural and optical characterization of mechanochemically synthesized CuSbS2 compounds
    Publication . Esperto, Luís; Figueira, Isabel; Mascarenhas, João; Silva, Teresa; Correia, J.B.; Neves, Filipe
    ABSTRACT: One of the areas of research on materials for thin-film solar cells focuses on replacing In and Ga with more earth-abundant elements. In that respect, chalcostibite (CuSbS2) is being considered as a promising environmentally friendly and cost-effective photovoltaic absorber material. In the present work, single CuSbS2 phase was synthesized directly by a short-duration (2 h) mechanochemical-synthesis step starting from mixtures of elemental powders. X-ray diffraction analysis of the synthesized CuSbS2 powders revealed a good agreement with the orthorhombic chalcostibite phase, space group Pnma, and a crystallite size of 26 nm. Particle-size characterization revealed a multimodal distribution with a median diameter ranging from of 2.93 mu m to 3.10 mu m. The thermal stability of the synthesized CuSbS2 powders was evaluated by thermogravimetry and differential thermal analysis. No phase change was observed by heat-treating the mechanochemically synthesized powders at 350 degrees C for 24 h. By UV-VIS-NIR spectroscopy the optical band gap was determined to be 1.41 eV, suggesting that the mechanochemically synthesized CuSbS2 can be considered suitable to be used as absorber materials. Overall, the results show that the mechanochemical process is a viable route for the synthesis of materials for photovoltaic applications.
  • Mechanochemical synthesis of tetrahedrite materials using mixtures of synthetic and ore samples collected in the Portuguese zone of the Iberian Pyrite Belt
    Publication . Neves, Filipe; Esperto, Luís; Figueira, Isabel; Mascarenhas, João; Salgueiro, Rute; Silva, Teresa; Correia, J.B.; Carvalho, Patricia Almeida; de Oliveira, Daniel Pipa Soares
    ABSTRACT: Considering that the synthesis of tetrahedrite-based materials usually uses high purity elements, the evaluation of the direct application of ore samples as raw materials for their synthesis is a pertinent issue. In the present study, multiphase synthetic tetrahedrite samples were mixed with tetrahedrite-tennantite ore samples (in weight ratios of 0.8/0.2, 0.5/0.5 and 0.2/0.8) to produce tetrahedrite-based materials by solid-state mechanochemical syn-thesis. The ore samples were obtained from the abandoned Barrig ̃ao mine dumps and from the Neves Corvo mine, both located in the Portuguese zone of the Iberian Pyrite Belt, whose main constituents were found to be As-rich tetrahedrite and tennantite-(Fe), respectively. Depending on the ore sample and on the mixture ratios, the displacement reactions occurring during the synthesis process gave rise to different phase transformation paths. For the ratios of 0.5/0.5 and 0.2/0.8, the mixtures with the Barrig ̃ao ore were found to consist of a single sulfide phase, tetrahedrite-tennantite-(Fe), plus quartz, while famatinite was also observed in the 0.8/0.2 mixture. Tetrahedrite-tennantite-(Fe) phase was the main constituent of all mixtures with the Neves Corvo ore, but in all of them other sulfide phases, famatinite-luzonite and pyrite, were also present in addition to quartz. Despite being dissimilar, these results are very promising and encouraging, by confirming the possible direct usage of ore samples and of dump material for the synthesis of tetrahedrite-based materials with all the potential environmental-economic gains that can be obtained.
  • Natural alternatives for thermoelectric materials [Resumo]
    Publication . Santos, Beatriz; Lopes, E.B.; Neves, Filipe; Gonçalves, António Pereira
  • The START Project: Creating a sustainable supply chain for green energy harvesting products by Powder Metallurgy
    Publication . Neves, Filipe; Vicenzi, Bruno; Bianchi, Alvise; Rosinski, M.
    ABSTRACT: Sustainable Energy Harvesting Systems Based on Innovative Mine Waste Recycling (START) is an Innovation Action project co-funded by the EU and its Horizon Europe programme. Using an advanced powder production and consolidation process, the project’s aim is to create a sustainable supply chain for green energy harvesting products by transforming sulphide materials from mining waste into sustainable high-added-value Powder Metallurgy components for tellurium-free thermoelectric (TE) devices. Here, the consortium members offer a comprehensive summary of START’s background, the innovative workflow developed, and its potential impact.
  • Thermoelectric Properties of Tetrahedrites Produced from Mixtures of Natural and Synthetic Materials
    Publication . 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, Filipe
    ABSTRACT: 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.
  • Processing of tetrahedrite-based thermoelectric materials using tetrahedrite-tennantite copper ores
    Publication . Neves, Filipe; Esperto, Luís; Figueira, Isabel; Mascarenhas, João; Salgueiro, Rute; Silva, Teresa; Correia, J.B.; de Oliveira, Daniel Pipa Soares; Almeida, P.
    ABSTRACT: Tetrahedrite-based compounds are considered a promising thermoelectric material. The tetrahedrite-tennantite series, that can be generically expressed as Cu6[Cu4(Fe,Zn)2](Sb,As)4S13, is one of the most abundant sulfosalt minerals in the earth’s crust. The Iberian Pyrite Belt (IPB), located in southern Portugal and Spain, is the host of the largest concentration of massive sulfide deposits worldwide, where the tetrahedrite-tennantite series mineral is one of the constituents. In this work we evaluate the effectiveness of combining synthetic tetrahedrite (ST) with tetrahedritetennantite ore samples (TTOS) in the mechanochemical synthesis (MCS) process of tetrahedrite based compounds. The ore samples were collected from two distinct deposits within the Portuguese part of the IPB, the Neves Corvo mine and the abandoned Barrigão copper mine. The ST, also produced by MCS, were mixed with the TTOS in different mass ratios ranging from 20-80%. The influence of the chemical composition and phase constitution of the ore samples and of the mixing ratios will be presented in relation to the micro-structural properties of the obtained materials. The results here described are part of a broader study dedicated to the development of energy-harvesting applications based on tetrahedrite.