Development of polymer wicks for the fabrication of bio-medical sensors

Polymer based wicking structures were fabricated by sintering powders of polycarbonate (PC), ultra-high molecular weight polyethylene and polyamide 12, aiming at selecting a suitable material for an innovative electroencephalography (EEG) bio-electrode. Preliminary experiments showed that PC based wicks displayed the best mechanical properties, therefore more detailed studies were carried out with PC to evaluate the influence of powder granulometry and processing parameters (pressure, temperature and time) on the mechanical properties, porosity, mean pore radius and permeability of the wicks. It was concluded that the mechanical properties are significantly enhanced by increasing the processing time and pressure, although at the expense of a significant decrease of porosity and mean pore diameter (and thus permeability), particularly for the highest applied pressures (74kPa). However, a good compromise between porosity/permeability and mechanical properties could be obtained by sintering PC powders of particle sizes below 500μm at 165°C for 5min, upon an applied pressure of 56kPa. Moreover, PC proved to be chemically stable in contact with an EEG common used disinfectant. Thus, wicking structures with appropriate properties for the fabrication of reusable bio-electrodes could be fabricated from the sintering of PC powders.

Probing dispersion and re-agglomeration phenomena upon melt-mixing of polymer-functionalized graphite nanoplates

A one-step melt-mixing method is proposed to study dispersion and re-agglomeration phenomena of the as-received and functionalized graphite nanoplates in polypropylene melts. Graphite nanoplates were chemically modified via 1,3-dipolar cycloaddition of an azomethine ylide and then grafted with polypropylene-graft-maleic anhydride. The effect of surface functionalization on the dispersion kinetics, nanoparticle re-agglomeration and interface bonding with the polymer is investigated. Nanocomposites with 2 or 10 wt% of as-received and functionalized graphite nanoplates were prepared in a small-scale prototype mixer coupled to a capillary rheometer. Samples were collected along the flow axis and characterized by optical microscopy, scanning electron microscopy and electrical conductivity measurements. The as-received graphite nanoplates tend to re-agglomerate upon stress relaxation of the polymer melt. The covalent attachment of a polymer to the nanoparticle surface enhances the stability of dispersion, delaying the re-agglomeration. Surface modification also improves interfacial interactions and the resulting composites presented improved electrical conductivity.

Tensile properties of polymer repair materials - effect of test parameters

In this research, five types of polymer repair materials were selected for investigation of the influence of sample shape, deformation rate and test temperature on the mechanical properties determined with an uniaxial tensile test. The results showed the clear effect of measurement conditions on tensile strength, elongation and modulus of elasticity. The highest tensile strength and modulus of elasticity were exhibited by epoxy resin for the filling of concrete cracks, which achieved 1% elongation. The lowest coefficient of dispersion characterized the results of tensile test carried out using dumbbell samples at a deformation rate of 50 mm/min. The effect of temperature varied with the material type.

Evaluation of the performance of recycled textile fibres in the mechanical behaviour of a gypsum and cork composite material

Given the need for using more sustainable constructive solutions, an innovative composite material based on a combination of distinct industrial by-products is proposed aiming to reduce waste and energy consumption in the production of construction materials. The raw materials are thermal activated flue-gas desulphurization (FGD) gypsum, which acts as a binder, granulated cork as the aggregate and recycled textile fibres from used tyres intended to reinforce the material. This paper presents the results of the design of the composite mortar mixes, the characterization of the key physical properties (density, porosity and ultrasonic pulse velocity) and the mechanical validation based on uniaxial compressive tests and fracture energy tests. In the experimental campaign, the influence of the percentage of the raw materials in terms of gypsum mass, on the mechanical properties of the composite material was assessed. It was observed that the percentage of granulated cork decreases the compressive strength of the composite material but contributes to the increase in the compressive fracture energy. Besides, the recycled textile fibres play an important role in the mode I fracture process and in the fracture energy of the composite material, resulting in a considerable increase in the mode I fracture energy.

Assessment of polymer-based nanocomposites biodegradability

The management of solid waste is a growing concern in many countries. Municipal solid waste is a major component of the total solid waste generated by society, and the composting of municipal solid waste has gained some attention even though a composting treatment for it is not yet widespread. It may not be realistic to replace large portions of these plastics with biodegradable materials, and it may be more important to separate plastics unsuitable for the composting process at the generating spots. However, for food packaging, there is still a great deal of interest in using biodegradable plastics that are difficult to sort at the generation spots. Under these circumstances, nanocomposites of biodegradable polymers as matrix and nanoparticles, that can be degraded along with organic wastes during composting could be a solution. Therefore, this chapter aims to give an overview on the biodegradability studies of bio-nanocomposites. It will focus on different polymers, nanocomposites containing different clay types and inorganic particles exposed under different environments.

Tailored magnetic and magnetoelectric responses of polymer-based composites

The manipulation of electric ordering with applied magnetic fields has been realized on magnetoelectric (ME) materials, however, their ME switching is often accompanied by significant hysteresis and coercivity that represents, for some applications, a severe weakness. To overcome this obstacle, this work focus on the development of a new type of ME polymer nanocomposites that exhibits tailored ME response at room temperature. The multiferroic nanocomposites are based on three different ferrite nanoparticles, Zn0.2Mn0.8Fe2O4 (ZMFO), CoFe2O4 (CFO) and Fe3O4 (FO), dispersed in a piezoelectric co-polymer poly(vinylindene fluoride-trifluoroethylene), P(VDF-TrFE), matrix. No substantial differences were detected on the time-stable piezoelectric response of the composites (≈ -28 pC.N−1) with distinct ferrite fillers and for the same ferrite content of 10wt.%. Magnetic hysteresis loops from pure ferrite nanopowders showed different magnetic responses. ME results of the nanocomposite films with 10wt.% ferrite content revealed that the ME induced voltage increases with increasing DC magnetic field until a maximum of 6.5 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.26 T, and 0.8 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.15T, for the CFO/P(VDF-TrFE) and FO/P(VDF-TrFE) composites, respectively. On the contrary, the ME response of the ZMFO/P(VDF-TrFE) exposed no hysteresis and high dependence on the ZMFO filler content. Possible innovative applications such as memories and information storage, signal processing, ME sensors and oscillators have been addressed for such ferrite/PVDF nanocomposites.

Effect of polymeric matrix on morphology and photoelectric properties of polymer-quantum dots nanocomposites

Recently, CdTe semiconductor quantum dots (QDs) have attracted great interest due to their unique properties [1]. Their dispersion into polymeric matrices would be very for several optoelectronics applications. Despite its importance, there has been relatively little work done on charge transport in the QD polymeric films [2], which is mainly affected by their structural and morphological properties. In the present work, polymer-quantum dot nanocomposites films based on optically transparent polymers in the visible spectral range and CdTe QDs with controlled particle size and emission wavelength, were prepared via solvent casting. Photoluminescent (PL) measurements indicate different emission intensity of the nanocomposites. A blue shift of the emission peak compared to that of QDs in solution occurred, which is attributed to the QDs environment changes. The morphological and structural properties of the CdTe nanocomposites were evaluated. Since better QDs dispersion was achieved, PMMA seemed to be the most promising matrix. Electrical properties measurements indicate an ohmic behavior.

Superhydrophobic surfaces as a tool for the fabrication of hierarchical spherical polymeric carriers

Hierarchical polymeric carriers with high encapsulation efficiencies are fabricated via a biocompatible strategy developed using superhydrophobic (SH) surfaces. The carries are obtained by the incorporation of cell/BSA-loaded dextran-methacrylate (DEXT-MA) microparticles into alginate (ALG) macroscopic beads. Engineered devices like these are expected to boost the development of innovative and customizable systems for biomedical and biotechnological purposes.

In-line rheo-optical microstructural characterization of complex polymer systems

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos.

Synthesis, physical and magnetic properties of BaFe12O19/P(VDF-TrFE) multifunctional composites

Composite films with filler microparticles of Barium ferrite dispersed within P(VDF-TrFE) as polymeric matrix have been prepared by solvent evaporation. The lowest BaFO content of 1% wt acts as a small defect within the polymeric matrix, reducing the values of the dielectric and mechanical properties of the pure P(VDF-TrFE). For filler contents up to a 20%, the BaFO filler reinforces the matrix and measured properties increase their values. This trend is not followed by the electrical conductivity. We extended the study to fibers composed by BaFe12O19 microparticles in a PVDF matrix. Due to the big size of BaFO particles (1 micron in diameter), proper fabrication of the fiber shaped composites has not been achieved. We found that true BaFO content are always lower than nominal ones. Results are discussed in terms of the influence of size and morphology of the BaFO particles on the initial properties of the polymeric matrix.

Effect of acid or alkaline catalyst and of different capping agents on the optical properties of CdS nanoparticles incorporated within a diureasil hybrid matrix

CdS nanoparticles (NPs) were synthesized using colloidal methods and incorporated within a diureasil hybrid matrix. The surface capping of the CdS NPs by 3-mercaptopropyltrimethoxysilane (MPTMS) and 3-aminopropyltrimethoxysilane (APTMS) organic ligands during the incorporation of the NPs within the hybrid matrix has been investigated. The matrix is based on poly(ethylene oxide)/poly(propylene oxide) chains grafted to a siliceous skeleton through urea bonds and was produced by sol–gel process. Both alkaline and acidic catalysis of the sol–gel reaction were used to evaluate the effect of each organic ligand on the optical properties of the CdS NPs. The hybrid materials were characterized by absorption, steady-state and time-resolved photoluminescence spectroscopy and High Resolution Transmission Electron Microscopy (HR-TEM). The preservation of the optical properties of the CdS NPs within the diureasil hybrids was dependent on the experimental conditions used. Both organic ligands (APTMS and MPTMS) demonstrated to be crucial in avoiding the increase of size distribution and clustering of the NPs within the hybrid matrix. The use of organic ligands was also shown to influence the level of interaction between the hybrid host and the CdS NPs. The CdS NPs showed large Stokes shifts and long average lifetimes, both in colloidal solution and in the xerogels, due to the origin of the PL emission in surface states. The CdS NPs capped with MPTMS have lower PL lifetimes compared to the other xerogel samples but still larger than the CdS NPs in the original colloidal solution. An increase in PL lifetimes of the NPs after their incorporation within the hybrid matrix is related to interaction between the NPs and the hybrid host matrix.

Quantum field theory approach to the optical conductivity of strained and deformed graphene

The computation of the optical conductivity of strained and deformed graphene is discussed within the framework of quantum field theory in curved spaces. The analytical solutions of the Dirac equation in an arbitrary static background geometry for one dimensional periodic deformations are computed, together with the corresponding Dirac propagator. Analytical expressions are given for the optical conductivity of strained and deformed graphene associated with both intra and interbrand transitions. The special case of small deformations is discussed and the result compared to the prediction of the tight-binding model.

Optical properties of zirconium oxynitride films: the effect of composition, electronic and crystalline structures

tThis work is devoted to the investigation of zirconium oxynitride (ZrOxNy) films with varied opticalresponses prompted by the variations in their compositional and structural properties. The films wereprepared by dc reactive magnetron sputtering of Zr, using Ar and a reactive gas mixture of N2+ O2(17:3).The colour of the films changed from metallic-like, very bright yellow-pale and golden yellow, for low gasflows to red-brownish for intermediate gas flows. Associated to this colour change there was a significantdecrease of brightness. With further increase of the reactive gas flow, the colour of the samples changedfrom red-brownish to dark blue or even to interference colourations. The variations in composition dis-closed the existence of four different zones, which were found to be closely related with the variationsin the crystalline structure. XRD analysis revealed the change from a B1 NaCl face-centred cubic zirco-nium nitride-type phase for films prepared with low reactive gas flows, towards a poorly crystallizedover-stoichiometric nitride phase, which may be similar to that of Zr3N4with some probable oxygeninclusions within nitrogen positions, for films prepared with intermediate reactive gas flows. For highreactive gas flows, the films developed an oxynitride-type phase, similar to that of -Zr2ON2with someoxygen atoms occupying some of the nitrogen positions, evolving to a ZrO2monoclinic type structurewithin the zone where films were prepared with relatively high reactive gas flows. The analysis carriedout by reflected electron energy loss spectroscopy (REELS) revealed a continuous depopulation of thed-band and an opening of an energy gap between the valence band (2p) and the Fermi level close to 5 eV.The ZrN-based coatings (zone I and II) presented intrinsic colourations, with a decrease in brightness anda colour change from bright yellow to golden yellow, red brownish and dark blue. Associated to thesechanges, there was also a shift of the reflectivity minimum to lower energies, with the increase of thenon-metallic content. The samples lying in the two last zones (zone III, oxynitride and zone IV, oxide films)revealed a typical semi-transparent-optical behaviour showing interference-like colourations only dueto the complete depopulation of the d band at the Fermi level. The samples lying in these zones presentedalso an increase of the optical bandgap from 2 to 3.6 eV.