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.

Melhoria da eficiência energética em edifícios dos anos 70: implementação de soluções sustentáveis low-tech e low-cost

Dissertação de mestrado em Construção e Reabilitação Sustentáveis

Avaliação de programas de inovação: a importância dos impactos indiretos

Programa Doutoral em Engenharia Industrial e de Sistemas

Ashbya gossypii beyond industrial riboflavin production: a historical perspective and emerging biotechnological applications

The filamentous fungus Ashbya gossypii has been safely and successfully used for more than two decades in the commercial production of riboflavin (vitamin B2). Its industrial relevance combined with its high genetic similarity with Saccharomyces cerevisiae together promoted the accumulation of fundamental knowledge that has been efficiently converted into a significant molecular and in silico toolbox for its genetic engineering. This synergy has enabled a directed and sustained exploitation of A. gossypii as an industrial riboflavin producer. Although there is still room for optimizing riboflavin production, the recent years have seen an abundant advance in the exploration of A. gossypii for other biotechnological applications, such as the production of recombinant proteins, single cell oil and flavour compounds. Here, we will address the biotechnological potential of A. gossypii beyond riboflavin production by presenting (a) a physiological and metabolic perspective over this fungus; (b) the molecular toolbox available for its manipulation; and (c) commercial and emerging biotechnological applications for this industrially important fungus, together with the approaches adopted for its engineering.

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.

Novel hybrid multifunctional magnetoelectric porous composite films

Novel multifunctional porous films have been developed by the integration of magnetic CoFe2O4 (CFO) nanoparticles into poly(vinylidene fluoride)-Trifuoroethylene (P(VDF-TrFE)), taking advantage of the synergies of the magnetostrictive filler and the piezoelectric polymer. The porous films show a piezoelectric response with an effective d33 coefficient of -22 pC/N-1, a maximum magnetization of 12 emu.g-1 and a maximum magnetoelectric coefficient of 9 mV.cm-1.Oe-1. In this way, a multifunctional membrane has been developed suitable for advanced applications ranging from biomedical to water treatment.

State of the art and open questions on cathode preparation based on carbon coated lithium iron phosphate

One important component with particular relevance in battery performance is the cathode, being one of the main responsible elements for cell capacity and cycle life. Carbon coated lithium iron phosphate, C-LiFePO4, active material is one of the most promising cathode materials for the next generation of large scale lithium ion battery applications and strong research efforts are being devoted to it, due to its excellent characteristics, including high capacity, ~170 mAh/g, and safety. This review summarizes the main developments on C-LiFePO4 based cathode film preparation and performance. The effect of the binder, conductive additive, relationship between active material-binder-conductive additive and drying step, in the electrode film fabrication and performance is presented and discussed. Finally, after the presentation of the cell types fabricated with C-LiFePO4 active material and their performance, some conclusions and guidelines for further investigations are outlined.

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.

Novel anisotropic magnetoelectric effect on δ-FeO(OH)/P(VDF-TrFE) multiferroic composites

The last decade has witnessed an increased research effort on multi-phase magnetoelectric (ME) composites. In this scope, this paper presents the application of novel materials for the development of anisotropic magnetoelectric (ME) sensors based on δ-FeO(OH)/P(VDF-TrFE) composites. The composite is able to precisely determine the amplitude and direction of the magnetic field. A new ME effect is reported in this study, as it emerges from the magnetic rotation of the δ-FeO(OH) nanosheets inside the piezoelectric P(VDF-TrFE) polymer matrix. δ-FeO(OH)/P(VDF-TrFE) composites with 1, 5, 10 and 20 δ-FeO(OH) filler weigh percentage in three δ-FeO(OH) alignment states (random, transversal and longitudinal) have been developed. Results shown that the modulus of the piezoelectric response (10-24 pC.N-1) is stable at least up to three months, the shape and magnetization maximum value (3 emu.g-1) is dependent on δ-FeO(OH) content and the obtained ME voltage coefficient, with a maximum of ≈0.4 mV.cm-1.Oe-1, is dependent on the incident magnetic field direction and intensity. In this way, the produced materials are suitable for innovative anisotropic sensor and actuator applications.

Gd2O3: Eu Nanoparticle-Based Poly(vinylidene fluoride) Composites for Indirect X-ray Detection

Polymer based scintillator composites have been fabricated by combining poly(vinylidene fluoride) (PVDF) and Gd2O3:Eu nanoparticles (50nm). PVDF has been used since it is a flexible and stable binder matrix and highly resistance to thermal and light deterioration. Gd2O3:Eu has been selected as scintillator material due to its wide band gap, high density and suitable visible light yield. The structural, mechanical, thermal and electrical characteristics of the composites were studied as a function of filler content, together with their performance as scintillator material. The introduction of Gd2O3:Eu nanoparticles into the PVDF matrix does not influence the morphology of the polymer or the degree of crystallinity. On the other hand, an increase of the Young´s modulus with respect to PVDF matrix is observed for filler contents of 0.1-0.75 wt.%. The introduction of Gd2O3:Eu into the PVDF matrix increases dielectric constant and DC electrical conductivity as well as the visible light yield in the nanocomposite, being this increase dependent upon Gd2O3:Eu content and X-ray input power. In this way, Gd2O3:Eu/PVDF composites shows suitable characteristics to be used as X-ray radiation transducers, in particular for large area applications.

Advances and future challenges in printed batteries

There is an increasing interest in thin and flexible energy storage devices to meet modern society needs for applications such as, radio frequency sensing, interactive packaging and other consumer products. Printed batteries comply these requirements and are an excellent alternative to conventional batteries for many applications. Flexible and micro-batteries are also included in the area of printed batteries whenever fabricated by printing technologies. The main characteristics, advantages, disadvantages, developments, and printing techniques of printed batteries are presented and discussed in this review. The state-of-art takes into account both the research and industrial levels. In the academic one, the research progress of printed batteries is summarized divided in lithium-ion battery (Li-ion), zinc-manganese dioxide (Zn-MnO2), and other battery types with emphasis on the different materials for anode, cathode and separator as well as in the battery design. With respect to the industrial state-of-art, materials, device formulations and manufacturing techniques are presented. Finally, the prospects and challenges of printed batteries are discussed.

Determination of the magnetostrictive response of nanoparticles via magnetoelectric measurements

It is successfully demonstrated that nanoparticle’s magnetostriction can be accurately determined based on the magnetoelectric effect measured on polymeric-composite materials. This represents a novel, simple and versatile method for the determination of particle’s magnetostriction at their nano-sized and dispersed state, which is, up to date, a difficult and imprecise task.

Ag-TiNx electrodes deposited on piezoelectric poly(vinylidene fluoride) for biomedical sensor applications

Electroactive polymers are one of the most interesting class of polymers used as smart materials in various applications, such as the development of sensors and actuators for biomedical applications in areas such as smart prosthesis, implantable biosensors and biomechanical signal monitoring, among others. For acquiring or applying the electrical signal from/to the piezoelectric material, suitable electrodes can be produced from Ti based coatings with tailored multifunctional properties, conductivity and antibacterial characteristics, through Ag inclusions. This work reports on Ag-TiNx electrodes, deposited by d. c. and pulsed magnetron sputtering at room temperature on poly(vinylidene fluoride), PVDF, the all-round best piezoelectric polymer.. Composition of the electrodes was assessed by microanalysis X-ray system (EDS - energy dispersive spectrometer). The XRD results revealed that the deposition conditions preserve the polymer structure and suggested the presence of crystalline fcc-TiN phase and fcc-Ag phase in samples with N2 flow above 3 sccm. According to the results obtained from SEM analysis, the coatings are homogeneous and Ag clusters were found for samples with nitrogen flow above 3 sccm. With increasing nitrogen flow, the sheet resistivity tend to be lower than the samples without nitrogen, leading also to a decrease of the piezoelectric response. It is concluded that the deposition conditions do significantly affect the piezoelectric polymer, which maintain its characteristics for sensor/actuator 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.

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.