Nonsolvent induced phase separation preparation of poly(vinylidene fluoride-co-chlorotrifluoroethylene) membranes with tailored morphology, piezoelectric phase content and mechanical properties

Poly(vinylidene fluoride-co-chlorotrifluoroethylene) – P(VDF-CTFE) membranes are increasingly interesting for a wide range of applications, including battery separators, filtration membranes and biomedical applications. This work reports on the morphology, hydrophobicity, thermal and mechanical properties variation of P(VDF-CTFE) membranes processed by nonsolvent induced phase separation technique (NIPS) as a function of the main processing parameters. All membranes show a porous structure composed of large spherulites, (interconnected) micropores and/or microvoids depending on the processing conditions used that in turn affect their hydrophobicity and mechanical properties. The degree of crystallinity of the membranes remains approximately constant with a value of about 15 %, except for the membranes immediately immersed in ethanol, which is of about 23 %. In turn, the crystalline phases present in the copolymer is mainly affected by the temperature and nonsolvent characteristics of the coagulation bath, the β-phase content ranging from 33 to 100 %, depending on those processing parameters. It was show that the temperature of water-based coagulation bath plays an important role in order to produce structurally uniform and homogeneous porous membranes, which is particularly important from the point of view of technological applications.

Poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) lithium-ion battery separator membranes prepared by phase inversion

Separator membranes based on poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) were prepared by solvent casting technique based on its phase diagram in N,Ndimethylformamide (DMF) solvent. The microstructure of the PVDF-CTFE separator membranes depends on the initial position (temperature and concentration) of the solution in the phase diagram of the PVDF-CTFE/DMF system. A porous microstructure is achieved for PVDF-CTFE membranes with solvent evaporation temperature up to 50 ºC for a polymer/solvent relative concentration of 20 wt%. The ionic conductivity of the separator depends on the degree of porosity and electrolyte uptake, the highest room temperature value being 1.5 mS.cm-1 for the sample with 20 wt% of polymer concentration and solvent evaporation temperature at 25 ºC saturated with 1 mol L-1 lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) in propylene carbonate (PC). This PVDF-CTFE separator membrane in Li/C-LiFePO4 half-cell shows good cyclability and rate capability, showing a discharge value after 50 cycles of 92 mAh.g-1 at 2 C, which is still 55% of the theoretical value. PVDF-CTFE separators are thus excellent candidates for high-power and safety lithium-ion batteries applications.

Phase morphology and crystallinity of poly(vinylidene fluoride)/poly(ethylene oxide) piezoelectric blend membranes

Polymer blends based on poly(vinylidene fluoride), PVDF and poly(ethylene oxide), PEO, with varying compositions have been prepared by solvent casting, the polymer blend films being obtained from solutions in dimethyl formamide at 70ºC. Under these conditions PVDF crystallizes from solution while PEO remains in the molten state. Then, PEO crystallizes from the melt confined by PVDF crystalls during cooling to room temperature. PVDF crystallized from DMF solutions adopt predominantly the electroactive β-phase (85%). Nevertheless when PEO is introduced in the polymer blend the β-phase content decreases slightly to 70%. The piezoelectric coefficient (d33) in pristine PVDF is -5 pC/N and decreases with increasing PEO content in the PVDF/PEO blends. Blend morphology, observed by electron and atomic force microscopy, shows the confinement of PEO between the already formed PVDF crystals. On the other hand the sample contraction when PEO is extracted from the blend with water (which is not a solvent for PVDF) allows proving the co-continuity of both phases in the blend. PEO crystallization kinetics have been characterized by DSC both in isothermal and cooling scans experiments showing important differences in crystalline fraction and crystallization rate with sample composition.

Variation of the physicochemical and morphological characteristics of solvent casted poly(vinylidene fluoride) along its binary phase diagram with dimethylformamide

Poly(vinylidene fluoride), PVDF, films and membranes were prepared by solvent casting from dimethylformamide, DMF, by systematically varying polymer/solvent ratio and solvent evaporation temperature. The effect of the processing conditions on the morphology, degree of porosity, mechanical and thermal properties and crystalline phase of the polymer were evaluated. The obtained microstructure is explained by the Flory-Huggins theory. For the binary system, the porous membrane formation is attributed to a spinodal decomposition of the liquid-liquid phase separation. The morphological features were simulated through the correlation between the Gibbs total free energy and the Flory-Huggins theory. This correlation allowed the calculation of the PVDF/DMF phase diagram and the evolution of the microstructure in different regions of the phase diagram. Varying preparation conditions allow tailoring polymer 2 microstructure while maintaining a high degree of crystallinity and a large β crystalline phase content. Further, the membranes show adequate mechanical properties for applications in filtration or battery separator membranes.

Ion exchange dependent electroactive phase content and electrical properties of poly(vinylidene fluoride)/Na(M)Y composites

Different metal-ion exchanged NaY zeolite, Na(M)Y, were used to prepare poly(vinylidene fluoride) based composites by solvent casting and melting crystallization. The effect of different metal ion-exchanged zeolites on polymer crystallization and electrical properties was reported. Cation-framework interactions and hydration energy of the cations determined that K+ is the most efficient exchanged ion in NaY zeolite, followed by Cs+ and Li+. The electroactive phase crystallization strongly depends on the ions present in the zeolite, leading to variations of the surface energy characteristics of the Na(M)Y zeolites and the polymer chain ability of penetration in the zeolite. Thus, Na(Li)Y and NaY induces the complete electroactive -phase crystallization of the crystalline phase of PVDF, while Na(K)Y only induces it partly and Na(Cs)Y is not able to promote the crystallization of the electroactive phase. Furthermore, different ion size/weigh and different interaction with the zeolite framework results in significant variations in the electrical response of the composite. In this way, iinterfacial polarization effects in the zeolite cavities and zeolite-polymer interface, leads to strong increases of the dielectric constant on the composites with lightest ions weakly bound to the zeolite framework. Polymer composite with Na(Li)Y show the highest dielectric response, followed by NaY and Na(K)Y. Zeolite Na(Cs)Y contribute to a decrease of the dielectric constant of the composite. The results show the relevance of the materials for sensor development.

Tailoring poly(vinylidene fluoride-co-chlorotrifluoroethylene) microstructure and physicochemical properties by exploring its binary phase diagram with dimethylformamide

Poly(vinylidene fluoride-co-chlorotrifluoroethylene), PVDF-CTFE, membranes were prepared by solven casting from dimethylformamide, DMF. The preparation conditions involved a systematic variation of polymer/solvent ratio and solvent evaporation temperature. The microstructural variations of the PVDF-CTFE membranes depend on the different regions of the PVDF-CTFE/DMF phase diagram, explained by the Flory-Huggins theory. The effect of the polymer/solvent ratio and solvent evaporation temperature on the morphology, degree of porosity, β-phase content, degree of crystallinity, mechanical, dielectric and piezoelectric properties of the PVDF-CTFE polymer were evaluated. In this binary system, the porous microstructure is attributed to a spinodal decomposition of the liquid-liquid phase separation. For a given polymer/solvent ratio, 20 wt%, and higher evaporation solvent temperature, the β-phase content is around 82% and the piezoelectric coefficient, d33, is - 4 pC/N.

Antibacterial properties of fibrous stents coated with silver oxide nanocoatings

Stents are rigid and perforated tubular structures, which are inserted into blood vessels in order to prevent or inhibit the constriction of blood flow, restoring the normal blood flow, when blood vessels are clogged, being used in 70% of angioplasties. These medical devices assume great importance in the treatment of cardiovascular diseases (CVD) which are the leading cause of death worldwide. In the European Union CVD account for 40% of deaths and assume an estimated annual cost of 196 billion euros[1]. Stents must possess certain requirements, in order to, adequately, perform its function, such as biocompatibility (so that its use does not c ause damage on the health of its user), mechanical strength, radiopacity (so that it is easy to view), longitudinal flexibility, ease of handling, corrosion resistance and having high strength and high radial expansion ability to recover. Stents can be made of different materials, but metals, particularly stainless steel, are the most common. However, metallic stents present several dRawbacks such as corrosion and restenosis, leading to health complications for the patient, or even death. In order to minimize these disadvantages, new materials, like fibrous materials, have been used [2]. Monofilaments present high potential for stents development because, in addition to its biocompatibility, these materials allow the application of various surface treatments, such as antibacterial coatings. Furthermore, monofilament exhibit excellent mechanical properties, like greater stiffness and good results when subjected to compression, tensile and bending forces, since these forces will be directly supported by the monofilament [3]. To minimize the reaction of the human body and Limit the adhesion of microorganisms to the stent surface, some coatings have been developed, including the use of novel metals with antimicrobial properties, like silver. The main objective of this study was the development of fibrous stents, incorporation of silver oxide nanocoating. For the development of the stent, polyester monofilaments with 0.27mm of diameter were used in braiding technology, with a mandrel diameter of 6mm and a braiding angle of 35⁰. The mechanical behaviour of the stent were evaluated by mechanical testing under longitudinal and radial compression, bending. The results of compressive strength tests are according with value from literature: 1.13 to 2.9 N for radial compression and 0. 16-5.28N to longitudinal compression. From literature is also possible to verify that stents must present 75% of unchanged diameter during the bending test and must possess a porosity between 70% and 80% [4]. The produced polyester stent presents values of 1.29N for radial compression, 0.23N for longitudinal compression, 80% of porosity and 85.5% of unchanged diameter, during bending tests. For the antibacterial functionalization, silver oxide nanocoatings were prepared, through reactive magnetron g, with an Ag target in an Ar +O2 atmosphere. In order to evaluate the nanostructure and morphology of the coatings, d ifferent technique s like X-ray diffraction (XRD), scanning electron microscopy (SEM) and and X- ray photoelectron spectroscopy (XPS were used. From the analyses of XRD it is possible to verify that the peaks corresponds to planes of Ag2 O and MATERIAIS 2015 Porto, 21-23 June, 2015 characterize a cubic phase. The presence of Ag2 O is corroborated by XPS spectrum, where it is possible to observe silver, not only, in oxide state, but a lso in mettalic state, and it is possible to verify the presence of silver clusters, confirmed by SEM analysis. Films’ roughness and topography, parameters influencing the wettability of the surface and microorganism adhesion, were measured by Atomic Force Microscopy (AFM), and it was observed that the roughness is very low (under 10 nm). Coatings’ hydrophobicity and surface tension parameters were determined by contact angle measurement, and it was verified the hydrophobic behavior of the coatings. For antibacterial tests were used Staphylococcus epidermidis strain (IE186) and Staphylococcus aureus(ATCC 6538), and halo inhibition zone tests were realized. Ag+release rates were studied by means of inductively coupled plasma mass spectrometry (ICP -MS). The obtained results suggest that silver oxide coatings do not modify significantly surface properties of the substrate, like hydrophobicity and roughness, and present antimicrobial properties for both bacteria used.

Effect of NaCl additive on solute-solvent interactions in aqueous polyethylene glycol-sodium sulfate two-phase systems

Abstract Partition behavior of eight small organic compounds and six proteins was examined in poly(ethylene glycol)-8000-sodium sulfate aqueous two-phase systems containing 0.215 M NaCl and 0.5 M osmolyte (sorbitol, sucrose, TMAO) and poly(ethylene glycol)-10000-sodium sulfate-0.215 M NaCl system, all in 0.01 M sodium phosphate buffer, pH 6.8. The differences between the solvent properties of the coexisting phases (solvent dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were characterized with solvatochromic dyes using the solvatochromic comparison method. Differences between the electrostatic properties of the phases were determined by analysis of partitioning of sodium salts of dinitrophenylated (DNP-) amino acids with aliphatic alkyl side-chain. The partition coefficients of all compounds examined (including proteins) were described in terms of solute-solvent interactions. The results obtained in the study show that solute-solvent interactions of nonionic organic compounds and proteins in polyethylene glycol-sodium sulfate aqueous two-phase system change in the presence of NaCl additive.

OnBoard reconfigurable battery charger for electric vehicles with traction-to-auxiliary mode

This paper proposes a single-phase reconfigurable battery charger for Electric Vehicle (EV) that operates in three different modes: Grid-to-Vehicle (G2V) mode, in which the traction batteries are charged from the power grid; Vehicle-to-Grid (V2G) mode, in which the traction batteries deliver part of the stored energy back to the power grid; and in Traction-to-Auxiliary (T2A) mode, in which the auxiliary battery is charged from the traction batteries. When connected to the power grid, the battery charger works with sinusoidal current in the AC side, for both G2V and V2G modes, and also regulates the reactive power. When the EV is disconnected from the power grid, the control algorithms are modified and the full-bridge AC-DC bidirectional converter works as a full-bridge isolated DC-DC converter that is used to charge the auxiliary battery of the EV, avoiding the use of an additional charger to accomplish this task. To assess the behavior of the proposed reconfigurable battery charger under different operation scenarios, a 3.6 kW laboratory prototype has been developed and experimental results are presented.

New control algorithm for single-phase series active power filter

This paper presents a single-phase Series Active Power Filter (Series APF) for mitigation of the load voltage harmonic content, while maintaining the voltage on the DC side regulated without the support of a voltage source. The proposed series active power filter control algorithm eliminates the additional voltage source to regulate the DC voltage, and with the adopted topology it is not used a coupling transformer to interface the series active power filter with the electrical power grid. The paper describes the control strategy which encapsulates the grid synchronization scheme, the compensation voltage calculation, the damping algorithm and the dead-time compensation. The topology and control strategy of the series active power filter have been evaluated in simulation software and simulations results are presented. Experimental results, obtained with a developed laboratorial prototype, validate the theoretical assumptions, and are within the harmonic spectrum limits imposed by the international recommendations of the IEEE-519 Standard.

Discriminação de fitofisionomias de floresta de várzea a partir do algoritmo Iterated Conditional Modes aplicado aos dados SAR/R99 (QUAD-POL/Banda L)

Utilizando-se dados do sensor aerotransportado SAR R99, adquiridos na banda L (1,28 GHz) em amplitude e com quatro polarizações (HH, VV, HV e VH), avaliou-se a distinção de fitofisionomias de floresta de várzea existentes nas Reservas de Desenvolvimento Sustentável Amanã e Mamirauá e áreas adjacentes, com a aplicação do algoritmo Iterated Conditional Modes (ICM) de classificação polarimétrica pontual/contextual. Os resultados mostraram que o uso das distribuições multivariadas em amplitude, conjuntamente com uma banda de textura, produziu classificações de qualidade superior àquelas obtidas com dados polarimétricos uni/bivariados. Esta abordagem permitiu a obtenção de um índice Kappa de 0,8963, discriminando as três classes vegetacionais de interesse, comprovando assim o potencial dos dados do SAR R99 e do algoritmo ICM no mapeamento de florestas de várzea da Amazônia.

Comunicação Android com câmaras ONVIF e gestão de Perfis de Media

Dissertação de mestrado integrado em Engenharia de Telecomunicações e Informática

Metabolic profiling and classification of propolis samples from Southern Brazil: an NMR-based platform coupled with machine learning

The chemical composition of propolis is affected by environmental factors and harvest season, making it difficult to standardize its extracts for medicinal usage. By detecting a typical chemical profile associated with propolis from a specific production region or season, certain types of propolis may be used to obtain a specific pharmacological activity. In this study, propolis from three agroecological regions (plain, plateau, and highlands) from southern Brazil, collected over the four seasons of 2010, were investigated through a novel NMR-based metabolomics data analysis workflow. Chemometrics and machine learning algorithms (PLS-DA and RF), including methods to estimate variable importance in classification, were used in this study. The machine learning and feature selection methods permitted construction of models for propolis sample classification with high accuracy (>75%, reaching 90% in the best case), better discriminating samples regarding their collection seasons comparatively to the harvest regions. PLS-DA and RF allowed the identification of biomarkers for sample discrimination, expanding the set of discriminating features and adding relevant information for the identification of the class-determining metabolites. The NMR-based metabolomics analytical platform, coupled to bioinformatic tools, allowed characterization and classification of Brazilian propolis samples regarding the metabolite signature of important compounds, i.e., chemical fingerprint, harvest seasons, and production regions.

Characterization of the oculomotor alterations in inicial phase of Multiple Sclerosis

Dissertação de mestrado em Advanced Optometry

Silicon nanowire arrays coupled with cobalt phosphide spheres as low-cost photocathodes for efficient solar hydrogen evolution

We demonstrate the first example of silicon nanowire array photocathodes coupled with hollow spheres of the emerging earth-abundant cobalt phosphide catalysts. Compared to bare silicon nanowire arrays, the hybrid electrodes exhibit significantly improved photoelectrochemical performance toward the solar-driven H2 evolution reaction.