JAQUELINE DE SOUZA DA SILVA

JAQUELINE DE SOUZA DA SILVA

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Identification of the polymer and electrode polarizations of Nafion dielectric spectrum
2019 - MATOS, B.R.; SILVA, J.S. da; SCHADE, U.; PUSKAR, L.; FONSECA, F.C.
SAXS signature of the lamellar ordering of ionic domains of perfluorinated sulfonic-acid ionomers by electric and magnetic field-assisted casting
2020 - SILVA, JAQUELINE S. da; CARVALHO, SABRINA G.M.; SILVA, RODRIGO P. da; TAVARES, ANA C.; SCHADE, ULRICH; PUSKAR, LJILJANA; FONSECA, FABIO C.; MATOS, BRUNO R.
At present, small angle X-ray scattering (SAXS) studies of perfluorinated sulfonic-acid ionomers (PFSAs) are unable to fully determine the true shape of their building blocks, as recent SAXS modelling predicts disk- and rod-like nanoionic domains as being equally possible. This scenario requires evidence-based findings to unravel the real shape of PFSA building blocks. Herein, a SAXS pattern signature for a lamellar nanophase separation of the ionic domains of Nafion is presented, backed by mid and far infrared spectroscopy (MIR and FIR) and wide angle X-ray scattering (WAXS) data of Nafion in different ionic forms, a broad range of ionic phase contents (EW ~ 859–42 252 g eq-1) and temperatures. The study indicates that the lamellar arrangement of the ionic domains is the most representative morphology that accounts for the physical properties of this ionomer. The lamellar SAXS reflections of Nafion are enhanced in electric and magnetic field-aligned membranes, as confirmed by atomic force microscopy (AFM). Electric and magnetic field-assisted casting of Nafion allowed producing nanostructured and anisotropic films with the lamellas stacked perpendicularly to the field vector, which is the direction of interest for several applications. Such nanostructured Nafion membranes are bestowed with advanced optical and proton transport properties, making them promising materials for solar and fuel cells.
Properties and DEFC tests of Nafion
2020 - MATOS, B.R.; GOULART, C.A.; TOSCO, B.; SILVA, J.S. da; ISIDORO, R.A.; SANTIAGO, E.I.; LINARDI, M.; SCHADE, U.; PUSKAR, L.; FONSECA, F.C.; TAVARES, A.C.
Nafion based composites are promising materials to improve the performance of direct ethanol fuel cells. In this work, composite membranes of Nafion and titanate nanotubes functionalized with sulfonic acid groups were prepared by melt-extrusion and tested in a direct ethanol fuel cell. Far and mid infrared spectroscopies evidenced the formation of ionic bridges between the sulfonic acid groups of both functionalized nanoparticles and the ionomer. Small angle X-ray scattering measurements revealed that the melt-extrusion method leads to an uniform distribution of the inorganic phase in the ionomer matrix. Such structural analysis indicated that the improved the proton conduction properties of the composites, even with the addition of a high concentration of functionalized nanoparticles, are an outcome of the synergistic ionic network due to the hydrid organic/inorganic proton conducting phases. However, an improvement of the fuel cell performance is observed for 2.5 wt% of functionalized titanate nanotubes, which is a result of the lower ethanol crossover and the plasticizing effect of the aliphatic segments of the organic moieties grafted at the surface of the titanate nanoparticles.
Efeito da relaxação do polímero na cristalinidade, fase iônica e formação de grupos sulfônicos anidridos no Nafion
2017 - MATOS, B.R.; SANTIAGO, E.I.; TOSCO, B.; REY, J.F.Q.; SILVA, J.S. da; SCHADE, U.; PUSKAR, L.; AZIZ, E.F.; FONSECA, F.C.
A relação entre as propriedades estruturais e elétricas de amostras de Nafion preparadas sob tratamento térmico em diferentes temperaturas (220 > T > 100 °C) foi investigada por espectroscopia no infravermelho (FTIR), espalhamento de raios-X em baixo ângulo (SAXS), calorimetria diferencial exploratória (DSC), análise dinâmico-mecânica (DMA) e espectroscopia de impedância (IS). Os resultados combinados de FTIR, SAXS, DSC, DMA revelaram que o tratamento térmico em baixas umidades relativas altera a morfologia do Nafion irreversivelmente devido a três características principais: i) o rearranjo das ligações de hidrogênio; ii) o reordenamento da fase cristalina; e iii) a formação de grupos sulfônicos anidridos. No entanto, a formação dos grupos anidridos é revertida pela reacidificação da membrana em soluções ácidas. O aspecto mais importante da dinâmica dos três processos descritos é que tais alterações são aceleradas acima de uma temperatura crítica: a temperatura de término da transição α do Nafion (Tendα ~ 160 °C). A transição α é atribuída ao enfraquecimento das interações eletrostáticas existentes entre os grupos sulfônicos do Nafion, que permitem a movimentação de longo alcance das cadeias poliméricas [1]. Este resultado indica que a maior dinâmica das cadeias do polímero em T > Tendα é o principal fator envolvido na modificação irreversível da morfologia do Nafion. As alterações da estrutura das ligações de hidrogênio afetaram negativamente as propriedades elétricas do Nafion. O aumento da temperatura de tratamento térmico reduz a condutividade protônica e aumenta a energia de ativação do transporte de cargas no Nafion. Tais resultados são relevantes para a preparação de conjuntos eletrodos-membrana (MEA) e para a operação de células a combustível de eletrólito polimérico (PEFC) em altas temperaturas [1].
Membranas nanoestruturadas de Nafion obtidas por conformação por moldagem assistida por campo elétrico e magnético
2019 - SILVA, JAQUELINE de S. da
Dentre os materiais aplicados como eletrólito em células a combustível de membrana de troca protônica (PEMFC do inglês Proton Exchange Membrane Fuel Cell), os ionômeros perfluorados, como o Nafion, são os mais promissores por possuírem alta condutividade protônica e estabilidade química. A estrutura do Nafion é composta pelo empacotamento eletrostático de agregados poliméricos cilíndricos que possuem maior condutividade protônica ao longo de seu comprimento. Destarte, o alinhamento dos agregados poliméricos do Nafion pode permitir o aumento da condutividade ao longo da espessura do filme, visando o aumento do desempenho da PEMFC. A proposta deste trabalho de mestrado é investigar os mecanismos de polarização do Nafion e aplicar os conhecimentos obtidos para confecção de filmes nanoestruturados por meio da aplicação do campo elétrico e magnético. Para isso, membranas de Nafion com diferentes concentrações de íons foram preparadas por substituição nucleofílica para estudar o mecanismo de polarização e, a partir dos resultados obtidos, membranas de Nafion foram nanoestruturadas por conformação por evaporação em molde (casting) assistido por campo elétrico e magnético. A caracterização da microestrutura e das propriedades elétricas das membranas poliméricas fabricadas foi realizada por meio da espectroscopia vibracional no infravermelho (FTIR), espalhamento de raios X em baixo ângulo (SAXS), espectroscopia de impedância elétrica (EIS) e microscopia de força atômica (AFM). Os resultados obtidos no estudo das membranas com diferentes valores de peso equivalente mostraram que os domínios iônicos do Nafion possuem alta polarizabilidade, a qual permitiu a nanoestruturação de tais domínios pela aplicação de campo elétrico e magnético de baixa intensidade. Os filmes de Nafion conformados pelo método de casting assistido por campo elétrico e magnético revelaram uma estrutura lamelar para o empacotamento dos domínios iônicos. Testes iniciais de células a combustível usando os eletrólitos fabricados por meio da aplicação do campo magnético indicaram um aumento pronunciado do desempenho.
An investigation of mechanical and thermal properties of polypropylene reinforced with different clays
2019 - MONTEIRO, ALEX S.; BARREIRA, DAILI A.S.; SILVA, JAQUELINE S.; OLIVEIRA, RENE R.; VALENZUELA-DIAZ, FRANCISCO R.; MOURA, ESPERIDIANA A.B.
Nowadays, environmental awareness and an increasing concern with the greenhouse effect have increased the interest in composite materials containing at least one of the components from natural origin. Natural clays seem to be a good alternative because they are environmentally acceptable, naturally abundant minerals, and due to their ability to intercalate and exfoliate in the polymer matrix led to an improvement in mechanical, thermal and barrier properties, compared to the neat polymer. This work presents an investigation of the effects of incorporation of two different clays on mechanical and thermal properties of polypropylene (PP) matrix. PP with 1.5–3.0 wt% of the Cloisite® (commercial clay), and light green clay (noncommercial Brazilian clay), was prepared by melt extrusion process. The neat PP and its nanocomposites were characterized by mechanical tests, SEM, DSC, TGA and XRD analyses. In addition, clay characterization by XRD has also been carried out.
The relation between the alpha/beta relaxation dynamics and the shape of ionomer building blocks
2018 - MATOS, B.R.; REY, J.F.Q.; MERINO, D.H.; SILVA, J.S. da; SCHADE, U.; PUSKAR, L.; FONSECA, F.C.
The relation between the alpha/beta relaxations and the shape of the building blocks of ionomer materials is a key factor for programming an important temperaturedependent property: the memory of shape [1,2,3]. However, the morphology of ionomers is indirectly obtained via modeling of small angle X-ray scattering (SAXS) data owing to the hardly accessible image characterization of the nanometric building blocks - micelle-like cylindrical polymeric aggregates (radius ~ 2 - 6 nm and length > 100 nm) [3]. Herein, broadband dielectric spectroscopy (BDS) measurements, free from electrode polarization effects, allowed identifying the time and temperature dependence of the polarization of different length scales of the ionomer matrix, and more importantly, by directly providing the aspect ratio of the radius and length of the polymeric aggregates for each desired temperature. This finding is essential for controlling the shape of ionomer based functional products under several stimuli conditions, thereby advancing remarkable applications, such as four dimensional (4D) printing and polymer electrolyte fuel cells.
Electrostatic interactions of Ionomer Films as Probed by Variable Temperature Synchrotron Infrared Spectroscopy
2018 - SILVA, J.S. da; MATOS, B.R.; SCHADE, U.; PUSKAR, L.; FONSECA, F.C.
The state of the art polymer electrolyte of Proton Exchange Membrane Fuel Cells (PEM), Nafion®, has poor mechanical and electrical properties at T > 100 °C. Specifically, long-term operation leads to irreversible performance losses that are related to an irreversible modification of the ionomer morphology above the temperature of alpha-transition (Talpha ~ 110 °C). Previous characterizations showed that the alpha-transition is dependent on the different states of covalent and ionic interactions among sulfonic acid groups, such as: ionic repulsions among RSO3-, dipolar attractions among RSO3H dipoles, hydrogen bonding of sulfonic groups with bulk and coordinated water molecules. The identification of both the functional groups interactions in the MIR bands and the “ion-hopping bands” in the FIR bands for annealed Nafion samples can give new insights into the role played by the ionic interactions on the alpha of ionomer membranes. Such approach for understanding the relationship between the dynamics of aplha-relaxation and Nafion morphology is missing in the literature, possibly due to the incipient number of FIR studies of Nafion. The central objective of this work is to advance the understanding of the chemical features involved during the aplha-transition of in situ annealed Nafion membranes with the high-resolution mid (MIR) and far (FIR) infrared spectroscopy using the IRIS beamline of BESSY II synchrotron light source. Herein, the effect of short-term annealing of Nafion at RH ~ 0% and selected temperatures below and above the alphatransition is presented. The comparison between SAXS and FTIR data of Nafion membranes annealed in situ revealed that the alpha-transition is due to the long range motion of the ionomer chains via weakening of electrostatic interactions of the ionomer functional groups.
Proton and cesium conductivity in perfluorosulfonate ionomers at low and high relative humidity
2017 - MATOS, BRUNO R.; SILVA, JAQUELINE S. da; SANTIAGO, ELISABETH I.; PARRA, DUCLERC F.; CARASTAN, DANILO J.; FLORIO, DANIEL Z. de; ANDRADA, HEBER E.; CARRERAS, ALEJO C.; FONSECA, FABIO C.
Nafion exhibits one of the highest proton conductivity at room temperature and it is the standard electrolyte of proton exchange membrane fuel cells (PEMFC). However, the temperature dependence of ionic conductivity of Nation is highly dependent on the measuring conditions and it is still a matter of debate. In the present study, detailed dielectric spectroscopy (DS) measurements in both dry (under N2 flow) and water-saturated conditions were carried out in a broad range of temperature and frequency. Such DS results were correlated to differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) data taken in similar conditions. The main results revealed that in samples conditioned in N2 flow (RH ~0%) the transport of both proton and cesiumions is coordinated with the dynamics of Nafion relaxations. In hydrated Nafion (proton form), conductivity measurements at different frequencies revealed two regimes: one at high-frequency, in which the Vogel-Tamman- Fulcher (VTF) law indicates a close relation between the polymer glass transition temperature Tg; and, a second one at low frequency, bearing great similarity to the transport observed in nearly dry samples. The reported experimental results contribute to disentangle the intricate transport properties of Nafion.
Structure and transport properties of annealed nafion membranes
2016 - MATOS, BRUNO R.; SILVA, JAQUELINE de S. da; FONSECA, FABIO C.
The relationship between electrical properties and the structural features of annealed Nafion samples was investigated by X-ray diffraction (XRD), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and impedance spectroscopy. Understanding of the observed effects on the proton conductivity due to annealing at controlled humidity at high temperature is crucial for improving the polymer electrolyte fuel cell (PEFC) at high operating temperatures (T > 100 °C) [1]. The experimental results reveal that membranes submitted to a heat treatment in the 100 – 200 °C temperature interval at low relative humidity (RH), display higher crystallinity and irreversibly shrinking of the ionic domains. However, the electrical properties of the polymer matrix were mostly affected by the irreversible destabilization of the ionic phase. The increase in crystallinity and shrinking of the hydrophilic domains reduce the ionomer conductivity. These features were reflected in the polymer electrolyte fuel cell (PEFC) tests in which the measured performance was lower for Nafion samples annealed at high T compared to pristine membranes. Such results are relevant for the preparation of membrane electrode assemblies as well as for the development of highperformance ionomer membranes.