Understanding the dispersion of fillers in polymer matrices

Understanding the mixing process of complex composite materials is fundamental in several industrial processes. For instance, the dispersion of fillers in polymer melt matrices is commonly employed to manufacture polymer composites, using a twin-screw extruder. The effectiveness of the filler dispersion depends not only on the complex flow patterns generated, but also on the polymer melt rheological behavior. Therefore, the availability of a numerical tool able to predict mixing, taking into account both fluid and particles phases would be very useful to increase the process insight, and thus provide useful guidelines for its optimization. In this work, a new Eulerian-Lagrangian numerical solver is developed OpenFOAM® computational library, and used to better understand the mechanisms determining the dispersion of fillers in polymer matrices. Particular attention will be given to the effect of the rheological model used to represent the fluid behavior, on the level of dispersion obtained. For the Eulerian phase the averaged volume fraction governing equations (conservation of mass and linear momentum) are used to describe the fluid behavior. In the case of the Lagrangian phase, Newton’s second law of motion is used to compute the particles trajectories and velocity. To study the effect of fluid behavior on the filler dispersion, several systems are modeled considering different fluid types (generalized Newtonian or viscoelastic) and particles volume fraction and size. The results obtained are used to correlate the fluid and particle characteristics on the effectiveness of mixing and morphology obtained.

Dielectric relaxation and ferromagnetic resonance in magnetoelectric (Polyvinylidene-fluoride)/ferrite composites

In this work the dielectric properties and ferromagnetic resonance of Polyvinylidene- uoride embedded with 10 wt. % of NiFe2O4 or Ni0.5Zn0.5Fe2O4 nanoparticles are presented. The mechanisms of the dielectric relaxation in these two composites do not differ from each other. For more precise characterization of the dielectric relaxation, a two dimensional distribution of relaxation times was calculated from the temperature dependencies of the complex dielectric permittivity. The results obtained from the 2D distribution and the mean relaxation time are found to be consistent. The dynamics of the dielectric permittivity is described by the Arrhenius law. The energy and attempt time of the dielectric relaxators lie in a narrow energy and time region thus proving that the single type chains of polymer are responsible for a dispersion. The magnetic properties of the composites were investigated using the fer- romagnetic resonance. A single resonance line was observed for both samples. From the temperature dependence (100 K - 310 K) of the resonance eld and linewidth, the origin of the observed line was attributed to the NiFe2O4 and Ni0.5Zn0.5Fe2O4 superparamagnetic nanoparticles. By measuring lms at dif- ferent orientations with respect to the external magnetic eld, the angular dependence of the resonance was observed, indicating the magnetic dipolar in-plane interactions.

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.

Magnetoelectric CoFe2O4/polyvinylidene fluoride electrospun nanofibres

Magnetoelectric 0-1 composites comprising CoFe2O4 (CFO) nanoparticles in polyvinylidene fluoride (PVDF) polymerfibre matrix have been prepared by electrospinning. The average diameter of the electrospun composite fibres D is ~ 325 nm, independently of nanoparticle content, and the amount of crystalline polar β phase is strongly enhanced when compared to pure PVDF polymer fibres. The piezoelectric response of these electroactive nanofibres is modified by an applied magnetic field, thus evidencing the magnetoelectric character of the CFO/PVDF 0-1 composites.

Hydrophobic/hydrophilic P(VDF-TrFE)/PHEA polymer blend membranes

Polymer blend membranes have been obtained consisting of a hydrophilic and a hydrophobic polymers distributed in co-continuous phases. In order to obtain stable membranes in aqueous environments, the hydrophilic phase is formed by a poly(hydrohyethyl acrylate), PHEA, network while the hydrophobic phase is formed by poly(vinylidene fluoride-co-trifluoroethylene) P(VDF-TrFE). To obtain the composites, in a first stage, P(VDF-TrFE) is blended with poly(ethylene oxyde) (PEO), the latter used as sacrificial porogen. P(VDF-TrFE)/PEO blend membranes were prepared by solvent casting at 70° followed by cooling to room temperature. Then PEO is removed from the membrane by immersion in water obtaining a P(VDF-TrFE) porous membrane. After removing of the PEO polymer, a P(VDF-TrFE) membrane results in which pores are collapsed. Nevertheless the pores reopen when a mixture of hydroxethyl acrylate (HEA) monomer, ethyleneglycol dimethacrylate (as crosslinker) and ethanol (as diluent) is absorbed in the membrane and subsequent polymerization yields hybrid hydrophilic/hydrophobic membranes with controlled porosity. The membranes are thus suitable for lithium-ion battery separator membranes and/or biostable supports for cell culture in biomedical applications.

Mechanical performance of natural fiber-reinforced composites for the strengthening of masonry

The growing concerns regarding the environmental impact generated by the use of inorganic materials in different fields of application increased the interest towards products based on materials with low environmental impact. In recent years, researchers have turned their attention towards the development of materials obtained from renewable sources, easily recoverable or biodegradable at the end of use. In the field of civil structures, a few attempts have been done to replace the most common composites (e.g. carbon and glass fibers) by materials less harmful to the environment, as natural fibers. This work presents a comprehensive experimental research on the mechanical performance of natural fibers for the strengthening of masonry constructions. Flax, hemp, jute, sisal and coir fibers have been investigated both from physical and mechanical points of view. The fibers with better performance were tested together with three different matrices (two of organic nature) in order to produce composites. These experimental results represent a useful database for understanding the potentialities of natural fibers as strengthening systems.

Design of assemblies based on polymer-coated quantum dots and organic dye

During last years, photophysical properties of complexes of semiconductor quantum dots (QDs) with organic dyes have attracted increasing interest. The development of different assemblies based on QDs and organic dyes allows to increase the range of QDs applications, which include imaging, biological sensing and electronic devices.1 Some studies demonstrate energy transfer between QDs and organic dye in assemblies.2 However, for electronic devices purposes, a polymeric matrix is required to enhance QDs photostability. Thus, in order to attach the QDs to the polymer surface it is necessary to chemically modify the polymer to induce electronic charges and stabilize the QDs in the polymer. The present work aims to investigate the design of assemblies based on polymer-coated QDs and an integrated acceptor organic dye. Polymethylmethacrylate (PMMA) and polycarbonate (PC) were used as polymeric matrices, and nile red as acceptor. Additionally, a PMMA matrix modified with 2-mercaptoethylamine is used to improve the attachment between both the donor (QDs) and the acceptor (nile red), as well as to induce a covalent bond between the modified PMMA and the QDs. An enhancement of the energy transfer efficiency by using the modified PMMA is expected and the resulting assembly can be applied for energy harvesting.

Optimization of magnetoelectric composites based on electroactive polymers for energy harvesting and sensor application

Tese de Doutoramento em Engenharia de Materiais.

Estudo da ligação entre componentes estruturais de GFRP (glass fiber reinforced polymer) e componentes estruturais em betão

Dissertação de mestrado integrado em Engenharia Civil

Enzymatic hydrophobic modification of jute fibers via grafting to reinforce composites

Horseradish peroxidase (HRP)/H2O2 system catalyzes the free-radical polymerization of aromatic compounds such as lignins and gallate esters. In this work, dodecyl gallate (DG) was grafted onto the surfaces of lignin-rich jute fabrics by HRP-mediated oxidative polymerization with an aim to enhance the hydrophobicity of the fibers. The DG-grafted jute fibers and reaction products of their model compounds were characterized by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results clearly indicated the grafting of DG to the jute fiber by HRP. Furthermore, the hydrophobicity of jute fabrics was determined by measuring the wetting time and static contact angle. Compared to the control sample, the wetting time and static contact angle of the grated fabrics changed from ~1 s to 1 h and from ~0° to 123.68°, respectively. This clearly proved that the hydrophobicity of jute fabrics improved considerably. Conditions of the HRP-catalyzed DG-grafting reactions were optimized in terms of the DG content of modified jute fabrics. Moreover, the results of breaking strength and elongation of DG-grafted jute/ polypropylene (PP) composites demonstrated improved reinforcement of the composite due to enzymatic hydrophobic modification of jute fibers.