High performance magnetoelectric nanocomposite morphologies for advanced applications

Tese de Doutoramento em Engenharia de MateriaisThe magnetoelectric (ME) effect is characterized by the variation of the electrical polarization of a material with an applied magnetic field and the variation of the magnetization of a material with an applied electric field. Single-phase materials with intrinsic ME effect are not generally used for practical applications since they typically show weak ME coupling at room temperatures. Such problem has been overcome by the development of ME composites. Strong ME effect at room temperature has been obtained, particularly in those composed by a piezoelectric and a magnetostrictive phase. In such materials, a strain is induced on the magnetostrictive phase once a magnetic field is applied to the composite. This strain is transmitted to the piezoelectric constituent, which undergoes a change in the electrical polarization. In an analogous way, the reverse effect can occur. The main objective of the thesis was the development of high performance polymer-based ME materials, that were characterized, optimized and their potential applications evaluated. Particulate ME composites were produced from materials with strong piezoelectric - poly(vinylidene fluoride) (P(VDF)) - and magnetostrictive - Cobalt iron oxide (CoFe2O4 - CFO) - responses in the form of film, membrane, fibers, and spheres. Related piezoelectric materials, such as the copolymer of P(VDF), poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)), and magnetic nanoparticles, such as magnetite (Fe3O4), goethite (δ-FeO(OH)) and CoFeO(OH), were also used. All developed morphologies show the presence of the ME effect. The studies on film morphology addressed the relevance of the magnetostrictive filler dispersion on ME composite response, suggesting that the use of surfactants or ultrasounds to improve the dispersion leads to the same ME response. The filler size and shape shows an important role on the ME measurements. Studies with Fe3O4 nanoparticle with sizes of 9, 30 and 50 nm within a P(VDF-TrFE) matrix show that the largest α31 = 0.97 mV.cm-1Oe-1 is obtained for the lowest nanoparticle size. The shape of the same filler was studied and the results shows that a rod shape, comparing with a spherical, nucleate the β-phase of P(VDF), due to the high interface interaction between the polymer and the filler. Anisotropic nanosheet fillers of δ-FeO(OH) and CoFeO(OH) were synthetized and evaluated for the preparation of ME composites. Thus, δ-FeO(OH) /P(VDF-TrFE) composites lead to a maximum ME response of 0.4 mV.cm-1.Oe-1, which depends on filler content, alignment state as well as on both incident magnetic field direction and magnitude. A new ME effect is proposed based on the magnetic rotation of the nanosheets inside the piezoelectric polymer matrix. New CoFeO(OH) highly magnetostrictive (λ = 507 ppm) and anisotropic nanostructures were synthesized by a coprecipitation method using a modified gas-slugs microfluidic system. CoFeO(OH) /P(VDF-TrFE) composites reveal an interfacial ME coupling strongly dependent on the angle between HDC and filler length direction, with a maximum α31 = 5.10 mV.cm-1.Oe-1. ME membranes were also produced in CFO/P(VDF-TrFE) composites. The porous morphology and ME response were evaluated. The porous composite shows piezoelectricity with an effective piezoelectric coefficient (d33) of -22 pC.N-1, a maximum magnetization of 12 emu.g-1 and a maximum ME coefficient of 9 mV.cm-1.Oe-1. ME nanofibers and microspheres of CFO/P(VDF) produced by electrospinning and electrospray technique, respectively, were studied and evaluated. The average diameter of the nanofibers is ≈325 nm, independently of filler content, and the amount of crystalline polar β-phase was strongly enhanced when compared to pure P(VDF) polymer fibers, due to the introduction of the magnetostrictive fillers. The piezoelectric response of these electroactive nanofibers was modified by an applied magnetic field, thus evidencing the ME character of the CFO/P(VDF) composites. The CFO nanoparticles content in the ME microspheres (3-7 µm diameter) reached values up to 27 wt.%, despite their concentration in the starting solution reaching values up to 70 wt.%. No relevant effect on β-phase content (≈60 %), crystallinity (40 %) and onset degradation temperature (460-465 °C) of the polymer matrix was observed. The ME microspheres show a maximum|d33|≈30 pC.N-1, leading to a ME response of ∆|d33|≈5 pC.N-1 obtained when a 220 mT DC magnetic field was applied. Its also shown that the interface between CFO and P(VDF) (0-55 %) has a strong influence on the ME response of the microspheres. The simplicity and the scalability of the processing methods used in the present work as well as the excellent ME response in a large variety of composite morphologies suggest a large application potential of the developed polymer-based ME composites in areas such as sensors and actuators and tissue engineering, among others.O efeito magnetoelétrico (ME) é caraterizado pela variação da polarização elétrica do material na presença de um campo magnético e pela variação da magnetização do material quando um campo elétrico é aplicado. Os materiais de fase única com o efeito ME intrínseco não são usualmente utilizados em aplicações uma vez que possuem fraco acoplamento ME à temperatura ambiente. Este problema é então ultrapassado com o desenvolvimento de compósitos MEs. Nestes, verifica-se um forte efeito ME obtido à temperatura ambiente, particularmente quando constituídos por uma fase piezoelétrica e outra magnetostritiva. Nestes materiais, a deformação é induzida na fase magnetostritiva quando um campo magnético é aplicado ao compósito. Essa deformação é transmitida ao constituinte piezoelétrico que provoca uma mudança na polarização elétrica do material. O efeito contrário pode ser também observado. O objetivo principal desta tese foi o desenvolvimento de materiais ME de base polimérica com alta performance, caracterização, otimização e avaliação para potencial aplicação. Foram produzidos compósitos ME particulados a partir de materiais com uma forte resposta piezoelétrica – poli(fluoreto de vinilideno) (P(VDF)) – e magnetostritiva – CoFe2O4 (CFO) – em forma de filme, membrana, fibras e esferas. O polímero piezoelétrico como o copolimero do P(VDF), poli(fluoreto de vinilideno-trifluoretileno) (P(VDF-TrFE)), e nanopartículas como Fe3O4, δ-FeO(OH) e CoFeO(OH) foram também estudados. Todos as morfologias desenvolvidas mostram a presença do efeito ME. Os estudos realizados na morfologia de filmes mostram a relevância da dispersão do material de reforço nos compósitos ME. Estes sugerem que tanto o uso de surfactantes como do ultrassons, para dispersar, têm a mesma influência nas medidas ME dos compósitos. O tamanho e a forma do material de reforço têm um papel importante nas medidas ME. Estudos com nanopartículas de Fe3O4 com tamanhos de 9, 30 e 50 nm no interior da matriz polimérica de P(VDF-TrFE), mostram que o maior α31 (0.97 mV.cm-1Oe-1) é obtido para a nanopartícula de menor tamanho. A influência da forma do material de reforço foi estudada e os resultados mostram que a forma de bastão, comparada com a esférica, nucleiam a fase β do P(VDF) devido à alta interação na interface entre o polímero e o material de reforço. Foram também sintetizadas e avaliadas as nanofolhas anisotrópicas de δ-FeO(OH) e CoFeO(OH) para a preparação de compósitos ME. Compósitos de δ-FeO(OH)/P(VDF-TrFE) com um máximo de ≈0.4 mV.cm-1.Oe-1, variam consoante a concentração do material de reforço, alinhamento e a direção e intensidade dos dois campos magnéticos incidentes. Um novo efeito ME é proposto baseado na rotação magnética das nanofolhas no interior da matriz polímérica. Sintetizou-se uma nova nanoestrutura anisotrópica de CoFeO(OH) com alta magnetostrição (λ = 507 ppm), pelo método de coprecipitação, com uma modificação no sistema microfluídico “gas-slugs”. Nanocompósitos de CoFeO(OH) /P(VDF-TrFE) revelam um acoplamento ME fortemente dependente do ângulo entre o HDC e o comprimento do CoFeO(OH), com um máximo α31 de 5.10 mV.cm-1.Oe-1. Membranas ME foram igualmente produzidas em compósitos CFO/P(VDF-TrFE). A morfologia porosa e a resposta ME foram avaliadas. O compósito poroso apresenta uma resposta piezoelétrica com um coeficiente piezoelétrico efetivo (d33) de -22 pC.N-1, uma magnetização máxima de 12 emu.g-1 e um coeficiente ME máximo de 9 mV.cm-1.Oe-1. Foram estudadas e avaliadas nanofibras e microesferas de CFO/P(VDF) produzidas por electrospinning e electrospray, respetivamente. O diâmetro médio das nanofibras foi de ≈325 nm, independentemente da quantidade de material de reforço e da quantidade da fase polar β, que é fortemente aumentada com a introdução do material de reforço magnetoestritivo quando comparada com as fibras puras de P(VDF). A resposta piezoelétrica das nanofibras eletroativas é modificada com a aplicação de um campo magnético, evidenciando assim o carácter ME do compósito CFO/P(VDF). Microesferas ME (3-7 µm de diâmetro) com nanopartículas de CFO foram preparadas com concentrações que chegam aos 27 % em peso, apesar de a solução inicial ter 70 %. Não foram verificadas alterações de fase β (≈60 %), cristalinidade (40 %) e temperatura de degradação onset (460-465 °C) do polímero. As microesferas ME apresentam um máximo |d33|≈30 pC.N-1, com a uma resposta ME de ∆|d33|≈5 pC.N-1 quando um campo magnético DC (220 mT) é aplicado. Verificou-se que a interface entre as nanopartículas de CFO e o P(VDF) (0-55 %) tem uma forte influência na resposta ME das microesferas. A simplicidade e a escalabilidade dos métodos de processamento apresentados neste trabalho, assim como a distinta resposta ME numa ampla variedade de morfologias, sugerem uma potencial aplicabilidade dos compósitos ME de base polimérica, em áreas como sensores e atuadores, engenharia de tecidos, entre outros

Reflexões teórico-práticas preliminares sobre o uso do ChatGPT como ferramenta criativa na publicidade

Este artigo tem como objetivo desenvolver reflexões teórico-práticas, a partir da empiria, sobre o uso do ChatGPT como ferramenta de criação de campanhas. Calibrando nossa perspectiva de investigação, inicialmente discutimos as bases dos processos de criação publicitária e destrinchamos as lógicas da inteligência artificial generativa. Caminhando para a experiência, usamos o ChatGPT para o desenho de campanhas de Natal para a Coca-Cola. Como resultados, destacamos algumas das principais limitações e as potencialidades da plataforma para a criatividade publicitária.This article aims to develop theoretical and practical considerations, based on empirical data, on the use of ChatGPT as a campaign creation tool. Calibrating our research perspective, we initially discuss the bases of advertising creation processes and unravel the logic of generative artificial intelligence. Moving on to experience, we used ChatGPT to design Christmas campaigns for Coca-Cola. As a result, we highlight some of the main limitations and potential of this platform for advertising creativity.Este artículo tiene como objetivo desarrollar reflexiones teóricas y prácticas, basadas em datos empíricos, sobre el uso de ChatGPT como herramienta de creación de campañas. Calibrando nuestra perspectiva de investigación, discutimos inicialmente las bases de los procesos de creación publicitaria y desentrañamos la lógica de la inteligencia artificial generativa. Pasando a la experiencia, usamos ChatGPT para diseñar campañas navideñas para Coca-Cola. Como resultado, destacamos algunas de las principales limitaciones y potencialidades de la plataforma para la creatividad publicitaria.

Reflexões teórico-práticas preliminares sobre o uso do ChatGPT como ferramenta criativa na publicidade

Este artigo tem como objetivo desenvolver reflexões teórico-práticas, a partir da empiria, sobre o uso do ChatGPT como ferramenta de criação de campanhas. Calibrando nossa perspectiva de investigação, inicialmente discutimos as bases dos processos de criação publicitária e destrinchamos as lógicas da inteligência artificial generativa. Caminhando para a experiência, usamos o ChatGPT para o desenho de campanhas de Natal para a Coca-Cola. Como resultados, destacamos algumas das principais limitações e as potencialidades da plataforma para a criatividade publicitária

Recent advances on materials for lithium-ion batteries

Environmental issues related to energy consumption are mainly associated with the strong dependence on fossil fuels. To solve these issues, renewable energy sources systems have been developed as well as advanced energy storage systems. Batteries are the main storage system related to mobility, and they are applied in devices such as laptops, cell phones, and electric vehicles. Lithium-ion batteries (LIBs) are the most used battery system based on their high specific capacity, long cycle life, and no memory effects. This rapidly evolving field urges for a systematic comparative compilation of the most recent developments on battery technology in order to keep up with the growing number of materials, strategies, and battery performance data, allowing the design of future developments in the field. Thus, this review focuses on the different materials recently developed for the different battery components—anode, cathode, and separator/electrolyte—in order to further improve LIB systems. Moreover, solid polymer electrolytes (SPE) for LIBs are also highlighted. Together with the study of new advanced materials, materials modification by doping or synthesis, the combination of different materials, fillers addition, size manipulation, or the use of high ionic conductor materials are also presented as effective methods to enhance the electrochemical properties of LIBs. Finally, it is also shown that the development of advanced materials is not only focused on improving efficiency but also on the application of more environmentally friendly materials.Funding grants UID/FIS/04650/2020, UID/EEA/04436/2020 and UID/QUI/0686/2020; and project PTDC/FIS-MAC/28157/2017. Financial support grants SFRH/BD/140842/2018 (J.C.B.) and Investigator FCT Contracts CEECIND/00833/2017 (R.G.) and 2020.04028.CEECIND (C.M.C.) Financial support ELKARTEK and PIBA (PIBA-2018-06) programs

Relação entre as desordens temporomandibulares e a presença de distúrbios respiratórios crônicos: uma revisão sistemática da literatura

Temporomandibular disorders (TMD) are a group of pathologies with direct implications for the understanding of comorbidities that may involve the stomatognathic system. This pathology has a multifactorial characteristic and, therefore, its possible relationship with systemic disorders, such as joint and psychological problems and, more specifically, chronic respiratory disorders (CRD) has been observed. The aim of this study was to conduct a systematic review in order to provide data on the relationship between TMD and CRD. Therefore, Medline, Collaboration Cochrane, Plataforma Capes, Biblioteca Virtual em Saúde, Scopus, Web of Science, Scielo were searched, covering the period from 2000 to 2021 and using the combination of the descriptors “Temporomandibular disorders and breathing and pain and mouth breathing”. After the search, which resulted in 698 documents found, only 15 were selected based on the pre-defined eligibility criteria. The relationship between the presence of TMD and the diagnosis of obstructive sleep apnea (OSA), as well as greater involvement by upper airway infections and postural changes in patients with a diagnosis of TMD in relation to patients without this diagnosis was established. The association between sleep disorders related to breathing, sleep quality and TMJ related pain was supported by some authors, highlighting the influence of these parameters on the quality of life of individuals. It was also observed that, even though the breathing pattern and its influences are a subject that is rarely mentioned in relation to TMD, this involvement can influence the individual's posture, which is directly related to the TMD symptomatology, mainly due to the occurrence of forward head postureIntrodução: As desordens temporomandibulares (DTM) são um grupo de patologias com implicação direta no entendimento das comorbidades que podem envolver o sistema estomatognático. Tal grupo patológico apresenta característica multifatorial e, por isso, tem sido observada sua possível relação com acometimentos sistêmicos, como problemas articulares, psicológicos e, mais especificamente, os distúrbios respiratórios crônicos (DRC). Objetivo: Conduzir uma revisão sistemática da literatura, utilizando ferramentas com validação metodológica, a fim de fornecer dados relevantes acerca da relação entre as DTM e os DRC. Metodologia: Foram pesquisadas as bases de dados MedLine/PubMed, Colaboração Cochrane, Plataforma Capes, Biblioteca Virtual em Saúde, Scopus, Web of Science e SciElo, cobrindo o período de 2000 a 2021 e utilizando a combinação dos descritores “temporomandibular disorders and breathing and pain and mouth breathing”. Resultados: Após a busca, que culminou em 698 documentos encontrados, apenas 12 foram selecionados a partir dos critérios de elegibilidade predefinidos. No tocante à relação entre a presença de DTM e o diagnóstico de apneia obstrutiva do sono (AOS), foram encontrados 45 indivíduos com essa associação, reportados por dois estudos. É relatado, também, acometimento por infecções de vias áreas superiores associadas às DTM (7.012 indivíduos reportados), além de diagnóstico de respiração bucal em pacientes que apresentavam o diagnóstico de DTM (30 indivíduos reportados). Conclusão: A associação entre desordens do sono relacionadas à respiração, respiração bucal, AOS e dor relacionada à ATM foi fundamentada por alguns autores, destacando a influência desses parâmetros na qualidade de vida dos indivíduos.  Observou-se, ainda, que esses acometimentos podem influenciar a postura do indivíduo, a qual está diretamente relacionada com a sintomatologia das DTM, principalmente pela ocorrência de anteriorização da cabeça

Cone geometry optimization and thermal behavior for lithium-ion battery separators

A 3D cone separator geometry for lithium-ion batteries has been optimized taking into account the increase of radius size of one side. Theoretical simulations have been carried out for evaluating the influence of radius size in the cone structure at different discharge rates (1 C and 60 C) in which it was also determined the produced ohmic heat. The value of the discharge capacity in the cone structure depends on the increases of the radius, which is correlated with the electrolyte volume and interface between free electrolyte/cathode. The optimum balance of these parameters is essential for obtaining higher battery performance through this geometry that can be used in the next generation of lithium-ion batteriesPortuguese Foundation for Science and Technology (FCT): UID/FIS/04650/2019, PTDC/CTMENE/5387/2014, UID/CTM/50025/2013, PTDC/FIS-MAC/28157/2017, grant SFRH/BPD/112547/2015 (C.M.C.) and contract CEECIND/00833/2017 (R.G.), including FEDER funds through the COMPETE 2020 Programme and National Funds through FCT. Financial support from the Basque Government Industry Department under the ELKARTEK and HAZITEK programs is also acknowledged. F. Miranda was also supported by Portuguese funds through the CIDMA - Center for Research and Development in Mathematics and Applications, and the Portuguese Foundation for Science and Technology (“FCT - Fundação para a Ciência e a Tecnologia”), within project UID/MAT/04106/201

Production of polymer filament-shaped piezoelectric sensors for e-textiles applications

This work aims at the development of piezoelectric materials for flexible sensors produced with various geometries, at low cost and high production rates, adequate for the industrial scale. In particular the filament form, appropriate for integration into textiles, is described, but other geometries, such as tape, are also being studied. The filaments are produced by co-extrusion of multiple layers with piezoelectric and electrically conductive polymer composites.Fundação para a Ciência e a Tecnologia (FCT) - PTDC/CTM/108801/200

Piezoelectric filaments produced by coextrusion

Considering the significant interest of both the academic and industrial communities in the fields of i/e-textiles (interactive/electronic textiles), the number of developed applications is far below the expected. This fact is mainly related to the difficulties on the development of production methodologies adequate to industrial scale processes. In this areas the integration of piezoelectric materials, that possess sensing/actuating capabilities, such as poly(vinylidene fluoride), PVDF, and can be processed using conventional processing techniques, is very promising and has encouraged a large number of research works. However, until now, most of the developed production methodologies are difficult to adapt to the industrial scale. This work reports recent developments achieved, in the framework of a research project, on the production of piezoelectric filament by coextrusion of PVDF and electrical conductive layers. The developed production methodology involves a conventional coextrusion line, for which a coextrusion die was designed to produce a multilayer filament. This filament comprises an inner layer of an electrically conductive Polypropylene grade and a middle layer of PVDF and is coated with an electrical conductive ink. The piezoelectric response of the produced filaments will be also presentedFundação para a Ciência e a Tecnologia (FCT)- FCT PTDC/CTM/108801/200

Theoretical simulation of different 3D separator geometries for lithium-ion batteries

The battery separator is an essential component of batteries and affects their cycling performance. In this work, the effect of different 3D geometries of the battery separator on battery performance was studied keeping the same volume. It was observed that the different geometries affect the cycling performance, the best geometry being the perforated one that cycled up to 90 C. The cycling performance is affected by parameters such as the separator thickness and the electrolyte volume. Through the control of the battery separator geometry it is possible to obtain high performance lithium-ion batteries.Portuguese Foundation for Science and Technology (FCT): UID/FIS/04650/2019, PTDC/CTMENE/5387/2014, UID/CTM/50025/2013, PTDC/FIS-MAC/28157/2017, grant SFRH/BPD/112547/2015 (C.M.C.) and contract CEECIND/00833/2017 (R.G.), including FEDER funds through the COMPETE 2020 Programme and National Funds through FCT. Financial support from the Basque Government Industry Department under the ELKARTEK and HAZITEK programs is also acknowledged. F. Miranda was also supported by Portuguese funds through the CIDMA - Center for Research and Development in Mathematics and Applications, and the Portuguese Foundation for Science and Technology (“FCT - Fundação para a Ciência e a Tecnologia”), within project UID/MAT/04106/2013

Características reprodutivas de onças-pintadas (Panthera onca) machos, mantidos em cativeiro

Ejaculate traits, testicular volume and plasma testosterone levels were determined once every two months for one year in 4 adult male jaguars (Panthera onca) housed at the São Paulo Zoo, SP, Brazil. Semen samples was collected by electroejaculation and analyzed for pH, total volume, motility (0-100%), status (0-5), total spermatozoa count and morphology. Blood samples was obtained by cephalic venipuncture immediately before the onset of electroejaculation and stored at -20ºC until assay of testosterone by RIA. Using a calliper, the length and width of each testis was measured and the values were combined to determine the testicular volume. Semen analyses demonstrated a high percentage of structurally abnormal sperm (mean = 51%) and low rates of motility (50.6%) and status (2.2). No correlation was found between semen traits, plasma testosterone and testicular volume (Spearman s test). No season variation was detected throughout the year for semen traits, plasma testosterone and testicular volume (p>0.05, Friedman s test). The results of this study suggest that the captive jaguars in Brazil are not seasonal, and that semen collections can be performed throughout the year without a perturbation in overall ejaculate quality. However, underlying causes of high percentages of structurally abnormal sperm, found in captive jaguars, need to be investigated mainly to improve semen quality.Quatro onças pintadas (Panthera onca), machos, adultos, mantidos no Zoológico de São Paulo (SP-Brasil), foram submetidos a avaliação seminal, quantificação hormonal e biometria testicular a cada dois meses pelo período de um ano. As amostras de sêmen foram obtidas por eletroejaculação e analisadas quanto ao pH, volume total, motilidade (0-100%), vigor (0-5), espermatozóides totais e morfologia. Amostras de sangue foram obtidas pela punção da veia cefálica imediatamente antes da eletroejaculação e o plasma foi estocado a -20ºC até a realização do radioimunoensaio para quantificação de testosterona. Comprimento e largura dos testículos direito e esquerdo foram obtidos com auxílio de paquímetro e os valores obtidos foram combinados para a obtenção de volume testicular. As amostras de sêmen mostraram elevado índice de espermatozóides morfologicamente anormais (média = 51%), baixos índice de motilidade (50,6%) e vigor (2,2). Não foi encontrada correlação entre as características seminais, níveis plasmáticos de testosterona e volume testicular (Teste de Correlação de Spearman). Não foi detectado efeito da estação durante o ano para qualidade espermática, testosterona sérica e volume testicular (p>0,05, Teste de Friedman). Os resultados sugerem que as onças pintadas mantidas em cativeiro não são sazonais e que a colheita e avaliação espermática podem ser realizadas em qualquer período do ano sem que haja perda na qualidade espermática. No entanto, as causas de elevado índice de espermatozóides morfologicamente anormais, encontrados neste estudo, devem ser investigadas.Universidade de São Paulo Faculdade de Medicina Veterinária e Zootecnia Departamento de Reprodução AnimalInstituto Brasileiro de Meio Ambiente CENAP Pró-CarnívorosAssociação Fundação Parque Zoológico de São PauloUniversidade de São Paulo Faculdade de Medicina Veterinária e Zootecnia Departamento de Medicina Veterinária Preventiva e Saúde AnimalUniversidade Federal de São Paulo (UNIFESP) Escola Paulista de Medicina Unidade EndócrinaUNIFESP, EPM, Unidade EndócrinaSciEL