Composite films of waterborne polyurethane and few-layer graphene-enhancing barrier, mechanical, and electrical properties

Graphene has excellent mechanical, thermal, and electrical properties. Graphene can serve as potential reinforcement in polymer-based nanocomposites. In order to achieve this goal, graphene has to be distributed homogeneously and dispersed throughout the polymer matrix, establishing a strong interface with the polymer. Solution mixing is an interesting method for the preparation of homogeneous nanocomposites, in particular when using environmentally friendly solvents such as water. The major difficulty met in the production of graphene/polymer composites concerns the preparation and stabilization of graphene in aqueous suspension. In the present work three different graphite-based materials, with different crystallinity and purity grades, were exfoliated in aqueous solution of an amphiphilic pyrene derivative, forming few-layer graphene (FLG). The FLG prepared was dispersed in waterborne polyurethane (WPU) to produce composite films. The composite films were produced by solvent casting and spray coating, forming free-standing films that were characterized in terms of its distribution of FLG through the composite, its permeability to water vapor, its electrical resistivity, and its mechanical properties. The studies demonstrated the influence of different factors on the composite film properties such as the use of graphite vs. FLG, the FLG lateral dimensions, and the FLG composition and composite preparation method.This work was funded by National Funds through the FCT—Portuguese Foundation for Science and Technology, Reference UID/CTM/50025/2013, and FEDER funds through the COMPETE 2020 Program under the project number POCI-01-0145-FEDER-007688. EC acknowledges the PhD grant SFRH/BD/87214/2012.info:eu-repo/semantics/publishedVersio

A Capacidade de rebrota das castanheiras.

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On the limits of Brans-Dicke spacetimes: a coordinate-free approach

We investigate the limit of Brans-Dicke spacetimes as the scalar field coupling constant omega tends to infinity applying a coordinate-free technique. We obtain the limits of some known exact solutions. It is shown that these limits may not correspond to similar solutions in the general relativity theory.Comment: LaTeX, 16 pp, report DF/UFPB/02-9

Dispersion of carbon nanotubes in poly(lactic acid)

Carbon nanotubes (CNT) present excellent mechanical, electrical and thermal properties, and are expected to impart these properties into their composites. However, the CNT are grown as entangled bundles that are difficult to disperse in polymer matrices, or even in solvents. Several approaches have been tried for the efficient dispersion of CNT in polymer matrices, ranging from the CNT chemical modification to the use of different mixing methods. Previous studies have shown that the resulting filler dispersion is strongly dependent on the characteristics of the melt mixing equipment [1]. It is also known that the dispersion level of nanofillers strongly affects the final nanocomposite properties [2]. The present work reports the optimization of the CNT dispersion in poly (lactic acid) (PLA) using a small-scale twin-screw extruder. The CNT were chemically modified for improved interaction with PLA. The effect of varying the mixing parameters on the dispersion level of the CNT and functionalized CNT was evaluated using optical and electron microscopy. The electrical resistivity and mechanical properties of the composites were measured. It was observed that the incorporation of 1% (weight) of CNT reduced the electrical resistivity of the composite to 400 Ohm.m, and that 3% CNT rendered the composite conductive, with an electrical resistivity of 0.6 Ohm.m.Fundação para a Ciência e a Tecnologia (FCT) - POCI/QUI/59835/2004, bolsa de doutoramento SFRH/BD/32189/2006

Dispersion and re-agglomeration of graphite nanoplates in polypropylene melts under controlled flow conditions

The kinetics of GnP dispersion in polypropylene melt was studied using a prototype small scale modular extensional mixer. Its modular nature enabled the sequential application of a mixing step, melt relaxation, and a second mixing step. The latter could reproduce the flow conditions on the first mixing step, or generate milder flow conditions. The effect of these sequences of flow constraints upon GnP dispersion along the mixer length was studied for composites with 2 and 10 wt.% GnP. The samples collected along the first mixing zone showed a gradual decrease of number and size of GnP agglomerates, at a rate that was independent of the flow conditions imposed to the melt, but dependent on composition. The relaxation zone induced GnP re-agglomeration, and the application of a second mixing step caused variable dispersion results that were largely dependent on the hydrodynamic stresses generated.Project Matepro – Optimizing Materials and Processes (NORTE-07-0124-FEDER-000037) by Programam Operacional Regional do Norte (ON.2

A comparative study of the dispersion of carbon nanofibres in polymer melts

The dispersion of carbon nanofibres (CNF) in a polymer matrix using two melt mixing methods is studied. Distributive and dispersive mixing were evaluated by optical and electron microscopy. The CNF were chemically modified to improve the interface with the matrix. The results showed that the two methods produced good distribution of the filler, but extensional stresses induced higher dispersion. The latter correlated well with a decrease in electrical resistivity. Also, the chemical modification largely improved the CNF/polymer interfaceFundação para a Ciência e a Tecnologia (FCT

Composites with polymer-grafted carbon nanotubes

Carbon nanotube (CNT)/polymer composites exhibit the processability advantages of plastics, while conveying electrical conductivity characteristics suitable for electric transport, or for sensing functionalities. The success of their application depends on the ability to homogeneously disperse the CNT in the polymer matrices to form a stable conductive network. The structural strength of the nanocomposite is also desirable, and may be a requirement. The chemical functionalization of the CNT is known to improve the mechanical properties of the nanocomposites, although it is observed to have a negative influence on the electrical conductivity. The present work reports the chemical modification of CNT to graft polycarbonate (PC) molecules to their surface, and the analysis of the CNT (as-received and PC-grafted) dispersion in PC by melt mixing using prototype equipment. The modified CNT were analyzed by thermogravimetry, X-ray photoelectron spectroscopy and scanning tunnelling microscopy, showing evidence for the formation of a polymer coating over the CNT. The nanocomposites were processed and reprocessed twice. The CNT dispersion was analyzed by optical microscopy using a similar analysis as described for PLA-grafted CNT [1], displaying considerable differences for CNT dispersion depending on their surface treatment. The electrical resistivity of the composites was measured, showing typically lower resistivity values for the composites with pristine CNT. The results also showed that resistivity of the composites with PC-grafted CNT may be considerably reduced depending on the processing steps.Fundação para a Ciência e a Tecnologia (FCT

Electrical and thermal properties of polyurethane/carbon nanotubes composites

The aim of this work was to study the effect of dispersing small amounts of CNT on the thermal diffusivity and electrical resistivity of PU/CNT composites. The PU nanocomposites were prepared with 0.5% and 1% weight of CNT. The composites were prepared by dispersion of the CNT in poly(propylene glycol) (PPG) followed by in situ polymerization, by mixing with 4,4′-Methylene di-p-phenyl diisocyanate (MDI). The PPG was characterized by an average molecular weight of 425 g/mol and a hydroxyl value 250 to 276 mg KOH/g. The MDI was characterized by a isocianate value (%NCO value) of 27.9-29.2. It was observed that the thermal diffusivity slightly increased with the addition of the CNT, but the results obtained were within the typical range for polymers (in the order of 10-8 m2/s). The electrical resistivity measured for the composites showed a large decrease after the addition of 0.5% and 1% of CNT. The electrical resistivity decreased 3 and 7 decades (from 109 .m to 106 and 103 .m) for 0.5 and 1% CNT composites, respectively. Thus, the composite bearing 1% of CNT dispersed in the PU presented semiconductor behaviour

Estimating the sustainability of carbon nanotube composites: reprocessing studies

Polylactide (PLA) has attracted particular attention in the area of environmentally degradable polymer materials. Some applications require the incorporation of a reinforcement material to produce a composite with specific properties. It was observed that PLA /carbon nanotube (CNT) composites present adequate properties for liquid sensing. The health risks involved in the use of carbon nanotubes are still under study, and thus the application of these materials must be planned with caution. From the point of view of environmental protection, recycling the CNT composites is the way to reduce these problems to the lower level possible, by maximizing they life cycle. The work presented reports the processing of PLA/CNT composite monofilaments, produced for sensing applications, and their reprocessing to form new monofilament composites. The monofilaments were reprocessed three times, and the tensile properties and electrical resistivity was measured. The melt flow index of the nanocomposites after each reprocessing step was measured. The thermal stability was evaluated by thermogravimetric analysis. It was observed that, although the melt flow index increased with reprocessing cycles, the tensile and electrical properties of the monofilaments produced after reprocessing were not affected, even after the fourth processing cycle. The thermal stability of the filaments was comparable after each processing cycle.Project Inteltex, FP

PEM Fuel Cell performance at sub-zero temperatures

In this work a study of the performance of a low power fuel cell at sub-freezing temperatures has been undertaken. Knowledge in this area is still scarce. After global characterization of the stack on a wide range of temperatures and relative humidity’s the behaviour at negative temperatures (-5ºC -10ºC, -15ºC) has been established. Furthermore, performance was evaluated after the cell was submitted to cycles from -25ºC to + 25ºC. At the end of 10 cycles only marginal loss in performance was registered, when testing at + 2.5ºC and + 25ºC. On the basis of the obtained results a strategy for start-up and shut-down has been designed in order to be implemented for operation at low temperatures. A failure analysis of the membrane and catalyst layers and GDLs is under way in order to evaluate material degradatio