Dielectric Relaxations and Conductivity of Crosslinked PVA/SSA/GO Composite Membranes for Fuel Cells

[EN] Composite membranes obtained from Poly(vinyl Alcohol) (PVA) with sulfosuccinic acid (SSA) as crosslinking agent, and two different proportions of graphene oxide (GO), were prepared to be used in Proton Exchange Membrane Fuel Cells (PEMFCs). The superficial micrographs from transmission electron microscopy (TEM) confirmed a good dispersion of GO. Fourier Transform Infrared spectroscopy (FTIR) was used to evaluate the final chemical structure. Differential Scanning Calorimetry (DSC) showed that glass transition and crystalline phase were not present in the cross-linked PVA/SSA/GO composites membranes. Thermogravimetric analysis (TGA) demonstrated that the addition of GO reduced the moisture content and increased the thermal stability of the membranes. The electrical properties of PVA/SSA and PVA/SSA/GO composite membranes and the effect of GO concentration were evaluated by means of dielectric spectra in a broad range of temperatures and frequencies. The dielectric permittivity of these membranes was significantly promoted at low filler concentration due to an interfacial polarization effect. From the analysis of the dielectric relaxation spectrum, it can be deduced that the origin of the associated molecular movements is intramolecular and occurs in the working range of the PMEFC. In addition, the direct current conductivity, the protonic conductivity, and the polarization currents were correlated to the power produced in a hydrogen monocell. It was observed that low and no high GO concentrations of filler in PVA/SSA composite membranes enhanced their performance. The systematic characterization procedure based on the study of dielectric spectra and conductivity allowed to establish a potential approach to control the addition of GO in the design of other composite membranes for PEMFC with improved properties.The authors would like to thank Dr. Roberto Teruel Juanes and Dr. Victor Saenz de Juano for their advice in the treatment of results. The authors are also thankful to Generalitat Valenciana and the European Social Fund for the Santiago Grisolia scholarship, GRISOLIA/2013/031, and the Spanish Ministry of Science and Innovation for the concession of Research Project ENE2014-53734-C2-1-R.González-Guisasola, C.; Ribes-Greus, A. (2018). Dielectric Relaxations and Conductivity of Crosslinked PVA/SSA/GO Composite Membranes for Fuel Cells. Polymer Testing. 67:55-67. https://doi.org/10.1016/j.polymertesting.2018.01.024S55676

Thermo-oxidative characterisation of the residues from persimmon harvest for its use in energy recovery processes

[EN] The residues from the harvest of persimmon fruit will be thermally valorised by means of high temperature reactions within a spouted bed reactor. With the aim to obtain valuable information for the design of the device, the thermo-chemical processes were simulated by multi-rate linear non-isothermal Thermogravimetric Analysis (TGA) using O-2 as carrier gas. In addition, a set of analyses were carried out using Ar as carrier gas in order to evaluate the influence of the atmosphere (oxidative or inert conditions) on the decomposition of the samples evaluating the reactions of pyrolysis. The release of gases was monitored by Evolved Gas Analysis (EGA) with in-line Fourier Transformed Infrared (FT-IR) analysis. The thermochemical reaction was mathematically described through the definition of the main kinetic parameters: activation energy (Ea), pre-exponential factor (In A) and model and order of reaction (n). The so-called kinetic triplet was calculated through the application of a methodology based on complementary isoconversional methods. These results will be the initial parameters that will help design the Spouted Bed Reactor and it is envisaged that they will be used in computer simulation software to achieve a better understanding of the process to obtain the optimum operational parameters. (C) 2016 Published by Elsevier B.V.Moliner, C.; Aguilar, A.; Bosio, B.; Arato, E.; Ribes-Greus, A. (2016). Thermo-oxidative characterisation of the residues from persimmon harvest for its use in energy recovery processes. Fuel Processing Technology. 152:421-429. https://doi.org/10.1016/j.fuproc.2016.07.008S42142915

Influence of the Molecular Weight on PVA/GO Composite Membranes for Fuel Cell Applications

Composite polymer electrolyte membranes were prepared with poly (vinyl alcohol) (PVA). Two different molecular weight (Mw), 67·103 and 130·103 g·mol−1 were selected, cross-linked with sulfosuccinic acid (SSA) and doped graphene oxide (GO). The effects on the membranes obtained from these polymers were characterized in order to evaluate the fuel cell performance. Electron microscopy showed a proper nanoparticle distribution in the polymer matrix. The chemical structure was evaluated by Fourier transform infrared spectroscopy. The absence of a crystalline structure and the enhancement on the thermal stability with the addition of 1% of GO was demonstrated by thermal characterization. Total transference number and protonic conductivity were correlated to the performance of a hydrogen fuel cell. Overall, a power increase in the composite membranes with lower molecular weight was observed. Shorter polymer chains may improve protonic conductivity and consequently the fuel cell performance

Degradation of Plasticised Poly(lactide) Composites with Nanofibrillated Cellulose in Different Hydrothermal Environments

In this study, bionanocomposite films based on poly(lactide) (PLA) plasticised with poly(ethylene glycol) (PEG) (7.5 wt%) and reinforced with various contents of nanofibrillated cellulose (NFC) (1, 3, 5 wt%) were prepared. The hydrothermal degradation was investigated through immersion in several aqueous environments at temperatures of 8, 23, 58, and 70 °C as a function of time (7, 15, 30, 60, 90 days). The effect of water immersion on the physicochemical properties of the materials was assessed by monitoring the changes in the morphology, thermo-oxidative stability, thermal properties, and molar mass through field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). The hydrothermal degradation behaviour was not critically affected regardless of the nanofibrillated cellulose content. All the materials revealed certain integrity towards water immersion and hydrolysis effects at low temperatures (8 and 23 °C). The low hydrothermal degradation may be an advantage for using these PLA biocomposites in contact with water at ambient temperatures and limited exposure times. On the other hand, immersion in water at higher temperatures above the glass transition (58 and 70 °C), leads to a drastic deterioration of the properties of these PLA-based materials, in particular to the reduction of the molar mass and the disintegration into small pieces. This hydrothermal degradation behaviour can be considered a feasible option for the waste management of PLA/PEG/NFC bionanocomposites by deposition in hot aqueous environments

Structure–Properties Relationship of Reprocessed Bionanocomposites of Plasticized Polylactide Reinforced with Nanofibrillated Cellulose

Bionanocomposites of polylactide (PLA), plasticized with poly(ethylene glycol) (PEG) (7.5 wt%, 400 and 1500 g/mol) and reinforced with nanofibrillated cellulose (NFC) (1, 3, and 5 wt%) were sequentially compounded, and injection and compression molded. All of the stages caused structural and morphological consequences, more relevant in the plasticized PLA, especially with low molar PEG. Small percentages of NFC (1 and 3 wt%) acted as crystalline nucleating agents and improved thermo-oxidative stability. Given the substantial degradation caused by (re)processing, a downgrading validation strategy was applied, assessing the mechanical and water contact performance during fictional first and second service life applications. After the first processing, PEG increased the ductility and reduced the strength and elastic modulus, while NFC buffered the fall in stiffness and increased rigidity compared to their PLA-PEG counterparts. Once reprocessed, PEG increased the water affinity of the blend, especially for low molar mass PEG. Low percentages of NFC (1 and 3 wt%) modulated water diffusivity and permeability, regardless of the water temperature. Overall, although reprocessing caused significant degradation, the mechanical valorization possibilities of these green bionanocomposites were proven, and are pointed out as sustainable candidates for food packaging or agricultural applications where modulated mechanical or water contact behaviors are required

New silica based adsorbent material from rice straw and its in-flow application to nitrate reduction in waters: Process sustainability and scale-up possibilities

[EN] This paper shows a particular example to move to a sustainable circular economical process from valorization of rice straw ashes by developing a green synthesis for obtaining a useful sub-product. This strategy can palliate negative effects of the agriculture waste practices on the environment and also the obtained silica reduced nitrate content in waters. It is demonstrated that the silica synthesis developed at lab was scalable more than a hundred times with good results. Adsorption studies of nitrate in standards and real well waters at lab scale and scaling-up provided similar results. Adsorption values near to 15 mg/g for nitrate standards and 8.5 mg/g for well water were obtained until achieving the initial nitrate concentration. Experimental breakthrough curves fitted to Thomas model, which gave similar results for adsorption capacities. The adsorption capacity was checked with that obtained by a commercial resin, providing improved results. The method at large scale was compared with industrial traditional methods and green adsorbents.The authors are grateful to EU (EASME LIFE and CIP ECO-Innovation) LIBERNITRATE. LIFE 16 ENV/ES/000419; EU FEDER and the Gobierno de Espana MCIU-AEI (CTQ2017-90082-P) and the Generalitat Valenciana (PROMETEO 2020/078) and EU FEDER-Generalitat Valenciana (ID-FEDER/2018/049) for the financial support received. H. R. Robles-Jimarez expresses his grateful to EU-LIBERNITRATE. L. Sanjuan-Navarro expresses his gratitude for the FPU-grant (MCIU-AEI) .Robles-Jimarez, H.; Sanjuan-Navarro, L.; Jornet-Martínez, N.; Primaz, C.; Teruel-Juanes, R.; Molins-Legua, C.; Ribes-Greus, A.... (2022). New silica based adsorbent material from rice straw and its in-flow application to nitrate reduction in waters: Process sustainability and scale-up possibilities. Science of The Total Environment. 805:1-12. https://doi.org/10.1016/j.scitotenv.2021.15031711280

Electron-hole correlation effects in the emission of light from quantum wires

We present a self-consistent treatment of the electron-hole correlations in optically excited quantum wires within the ladder approximation, and using a contact potential interaction. The limitations of the ladder approximation to the excitonic low-density region are largely overcome by the introduction of higher order correlations through self consistency. We show relevance of these correlations in the low-temperature emission, even for high density relevant in lasing, when large gain replaces excitonic absorption.Comment: 4 paes 3 figure

Mechanical and thermal performance of PLA and PHBV based biopolymers as potential alternatives to PET

[EN] The evaluation of the mechanical and thermal properties of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polylactide (PLA) and their biocomposites (containing 30%wt of sisal in their composition) has been studied and compared to poly(ethylene terephthalate) (PET). The addition of sisal to the biopolymeric matrix increased the elastic stiffness of the bio-composites achieving a performance which is comparable to PET. All biocomposites presented lower traction resistance and elongation values respect to PET.The addition of natural fibers improved the thermal stability of PHBV-based samples. The trigger of decomposition happened at lower temperatures respect to PET, but always far above their melting point ensuring a good performance of the composites at high processing temperatures. The apparent activation energies for the biocomposites in inert conditions respect to those for PET indicates a more suitable scenario from the energetic valorisation point of view.Moliner, C.; Badia, J.; Bosio, B.; Arato, E.; Lagazzo, A.; Capurro, M.; Ribes-Greus, A. (2017). Mechanical and thermal performance of PLA and PHBV based biopolymers as potential alternatives to PET. Chemical Engineering Transactions. 57:1417-1422. https://doi.org/10.3303/CET1757237S141714225

Poly (lactic acid)/D-limonene/ZnO bio-nanocomposites with antimicrobial properties

Antimicrobial films of poly (lactic acid) (PLA)/D-limonene/zinc oxide (ZnO)-based bio-nanocomposites were prepared via melt compounding and subsequent thermocompression. D-limonene was incorporated at concentrations of 10 or 20 wt%, and ZnO pure nanoparticles and those organically modified with oleic acid (O-ZnO), with an average diameter of 13.5 nm, were included at concentrations of 3, 5, and 8 wt%. The plasticizing effect of D-Limonene was corroborated by a decrease in the glass transition temperature compared to pure PLA. The presence of ZnO and O-ZnO in the PLA matrix promoted a slight increase in the degree of crystallinity due to its nucleant performance. Although ZnO and O-ZnO induced lower thermal stability and slightly decreased microhardness in the composites, excellent antimicrobial performance was demonstrated. Both ZnO and O-ZnO nanocomposites reached 99.9% of effectiveness for nanoparticles content above 5 wt%, regardless of the source of irradiation, D-limonene concentration, and nanoparticle modification. Therefore, these bio-nanocomposites will allow for future advances in sustainable antimicrobial materials for the medical or food packaging fields.DICYT, Grant/Award Number: Project 022041ZR_POSTDOCT; Fondo Nacional de Desarrollo Científico y Tecnológico,Grant/Award Numbers: 1170226, 320029