Modelling the Mechanical Behavior of Polymer-Based Nanocomposites

Molecular dynamics simulations were employed to analyze the mechanical properties of polymer-based nanocomposites with varying nanofiber network parameters. The study was focused on nanofiber aspect ratio, concentration and initial orientation. The reinforcing phase affects the behavior of the polymeric nanocomposite. Simulations have shown that the fiber concentration has a significant effect on the properties, with higher loadings resulting in higher stress levels and higher stiffness, matching the general behavior from experimental knowledge in this field. The results also indicate that, within the studied range, the observed effect of the aspect ratio and initial orientation is smaller than that of the concentration, and that these two parameters are interrelated.

Síntese e fotosensibilização de nanotubos de titanatos

Nesta tese é descrita a preparação de nanotubos de titanatos (TNT) via síntese hidrotérmica alcalina, usando uma nova metodologia que evita a utilização de TiO2 cristalino como precursor. Foi estudada a influência da substituição sódio/protão na estrutura, morfologia e propriedades ópticas dos materiais preparados. Os resultados mostraram que a substituição Na+ → H+ resulta numa redução na distância intercamadas dos TNTs, tendo sido medidos valores entre 1.13±0.03 nm e 0.70±0.02 nm para aquele parâmetro. O comportamento óptico dos TNTs foi estudado na região UV-vis, estimando-se um hiato óptico de energia 3.27±0.03 eV para a amostra com maior teor de sódio enquanto que para a amostra protonada foi determinado um valor de 2.81±0.02 eV. Estes valores mostram que a troca iónica Na+ → H+ teve influência no desvio da banda de absorção dos TNTs para a região do visível próximo. A actividade fotocatalítica dos TNTs na degradação do corante rodamina 6G (R6G) foi posteriormente estudada. Verificou-se que, apesar de a amostra com maior teor de sódio ter sido a que exibiu maior capacidade para adsorver o R6G, foi a amostra protonada que apresentou a actividade catalítica mais elevada na fotodegradação deste corante. Numa segunda fase, e com o objectivo de preparar novos materiais nanoestruturados fotosensíveis, procedeu-se à decoração dos TNTs protonados com semicondutores (SC) nanocristalinos usando um método novo. Para o efeito os TNTs foram decorados com nanocristalites de ZnS, CdS e Bi2S3. Foi estudada a influência do tipo de semicondutor na estrutura, morfologia e propriedades ópticas dos SC/TNTs obtidos. Verificou-se que, para qualquer dos semicondutores usados no processo de decoração, a estrutura dos TNTs é preservada e não ocorre segregação do SC. Verificou-se ainda que a morfologia dos nanocompósitos preparados depende fortemente da natureza do semicondutor. No que respeita ao comportamento óptico destes materiais, foram determinados hiatos ópticos de energia 3.67±0.03 eV, 2.47±0.03 eV e 1.35±0.01 eV para as amostras ZnS/TNT, CdS/TNT e Bi2S3/TNT, respectivamente. Estes resultados mostram que através do processo de decoração de TNTs com semicondutores podem ser preparados materiais nanocompósitos inovadores, com propriedades ópticas novas e/ou pré-definidas numa gama alargada do espectro electromagnético.

Structural and optical studies of Au doped titanium oxide films

Thin films of TiO2 were doped with Au by ion implantation and in situ during the deposition. The films were grown by reactive magnetron sputtering and deposited in silicon and glass substrates at a temperature around 150 degrees C. The undoped films were implanted with Au fiuences in the range of 5 x 10(15) Au/cm(2)-1 x 10(17) Au/cm(2) with a energy of 150 keV. At a fluence of 5 x 10(16) Au/cm(2) the formation of Au nanoclusters in the films is observed during the implantation at room temperature. The clustering process starts to occur during the implantation where XRD estimates the presence of 3-5 nm precipitates. After annealing in a reducing atmosphere, the small precipitates coalesce into larger ones following an Ostwald ripening mechanism. In situ XRD studies reveal that Au atoms start to coalesce at 350 degrees C, reaching the precipitates dimensions larger than 40 nm at 600 degrees C. Annealing above 700 degrees C promotes drastic changes in the Au profile of in situ doped films with the formation of two Au rich regions at the interface and surface respectively. The optical properties reveal the presence of a broad band centered at 550 nm related to the plasmon resonance of gold particles visible in AFM maps. (C) 2011 Elsevier B.V. All rights reserved.

Structural Color and Iridescence in Transparent Sheared Cellulosic Films

Shear transparent cellulose free-standing thin films can develop iridescence similar to that found in petals of the tulip Queen of the Night. The iridescence of the film arises from the modulation of the surface into bands periodically spread perpendicular to the shear direction. Small amounts of nanocrystalline cellulose (NCC) rods in the precursor liquid-crystalline solutions do not disturb the optical properties of the solutions but enhance the mechanical characteristics of the films and affects their iridescence. Smaller bands periodicity, not affected by the NCC rods, slightly deviated from the shear direction is also observed. NCCs are crucial to tune and understand the film's surface features formation. Our findings could lead to new materials for application in soft reflective screens and devices.

Synthesis of titanate nanofibers co-sensitized with ZnS and Bi2S3 nanocrystallites and their application on pollutants removal

The synthesis of nanocomposite materials combining titanate nanofibers (TNF) with nanocrystalline ZnS and Bi2S3 semiconductors is described in this work. The TNF were produced via hydrothermal synthesis and sensitized with the semiconductor nanoparticles, through a single-source precursor decomposition method. ZnS and Bi2S3 nanoparticles were successfully grown onto the TNF's surface and Bi2S3-ZnS/TNF nanocomposite materials with different layouts. The samples' photocatalytic performance was first evaluated through the production of the hydroxyl radical using terephthalic acid as probe molecule. All the tested samples show photocatalytic ability for the production of this oxidizing species. Afterwards, the samples were investigated for the removal of methylene blue. The nanocomposite materials with best adsorption ability were the ZnS/TNF and Bi2S3ZnS/TNF. The dye removal was systematically studied, and the most promising results were obtained considering a sequential combination of an adsorption-photocatalytic degradation process using the Bi2S3ZnS/TNF powder as a highly adsorbent and photocatalyst material. (C) 2015 Elsevier Ltd. All rights reserved.

Organic-inorganic nanostructured multilayers for calcium phosphate biomineralization

The weak fixation of biomaterials within the bone structure is one of the major reasons of implants failures. Calcium phosphate (CaP) coatings are used in bone tissue engineering to improve implant osseointegration by enhancing cellular adhesion, proliferation and differentiation, leading to a tight and stable junction between implant and host bone. It has also been observed that materials compatible with bone tissue either have a CaP coating or develop such a calcified surface upon implantation. Thus, the development of bioactive coatings becomes essential for further improvement of integration with the surrounding tissue. However, most of current applied CaP coatings methods (e.g. physical vapor deposition), cannot be applied to complex shapes and porous implants, provide poor structural control over the coating and prevent incorporation of bioactive organic compounds (e.g. antibiotics, growth factors) because of the used harsh processing conditions. Layer-by-layer (LbL) is a versatile technology that permits the building-up of multilayered polyelectrolyte films in mild conditions based on the alternate adsorption of cationic and anionic elements that can integrate bioactive compounds. As it is recognized in natureâ s biomineralization process the presence of an organic template to induce mineral deposition, this work investigate a ion based biomimetic method where all the process is based on LbL methodology made of weak natural-origin polyelectrolytes. A nanostructured multilayer component, with 5 or 10 bilayers, was produced initially using chitosan and chondroitin sulphate polyelectrolyte biopolymers, which possess similarities with the extracellular matrix and good biocompatibility. The multilayers are then rinsed with a sequential passing of solutions containing Ca2+ and PO43- ions. The formation of CaP over the polyelectrolyte multilayers was confirmed by QCM-D, SEM and EDX. The outcomes show that 10 polyelectrolyte bilayer condition behaved as a  better site for initiating the formation of CaP as the precipitation occur at earlier stages than in 5 polyelectrolyte bilayers one. This denotes that higher number of bilayers could hold the CaP crystals more efficiently. This work achieved uniform coatings that can be applied to any surface with access to the liquid media in a low-temperature method, which potentiates the manufacture of effective bioactive biomaterials with great potential in orthopedic applications.

Microinjection molding of polyamide 6/carbon nanotube composites

Microinjection molding of polymer composites with carbon nanotubes (CNT) requires previous production of the nanocomposites, often by melt extrusion. Each processing step has a thermo-mechanical effect on the polymer melt, conveying different properties to the final product. In this work, polyamide 6 and its composites with pristine and functionalized CNT (f-CNT) were processed by a mini twin-screw extrusion, followed by microinjection molding. The morphology induced on the polymer by each process was analyzed by differential scanning calorimetry and wide angle X-ray diffraction. Calorimetric analysis showed a secondary crystallization for the microinjected materials, absent for the extruded materials. The characterization of microinjected polyamide 6 by X-ray diffraction revealed a large contribution of the c phase to the total crystallinity, mainly in the skin region, while the nanocomposites and extruded materials were characterized by a larger contribution of the a phase. Functionalization of CNT did not affect significantly the polymer morphology compared to composites with pristine CNT.

Improvign mixing processes with the help of numerical tools

In several industrial applications, highly complex behaviour materials are used together with intricate mixing processes, which difficult the achievement of the desired properties for the produced materials. This is the case of the well-known dispersion of nano-sized fillers in a melt polymer matrix, used to improve the nanocomposite mechanical and/or electrical properties. This mixing is usually performed in twin-screw extruders, that promote complex flow patterns, and, since an in loco analysis of the material evolution and mixing is difficult to perform, numerical tools can be very useful to predict the evolution and behaviour of the material. This work presents a numerical based study to improve the understanding of mixing processes. Initial numerical studies were performed with generalized Newtonian fluids, but, due to the null relaxation time that characterize this type of fluids, the assumption of viscoelastic behavior was required. Therefore, the polymer melt was rheologically characterized, and, a six mode Phan-Thien-Tanner and Giesekus models were used to fit the rheological data. These viscoelastic rheological models were used to model the process. The conclusions obtained in this work provide additional and useful data to correlate the type and intensity of the deformation history promoted to the polymer nanocomposite and the quality of the mixing obtained.

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.

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.

High-temperature polymer based magnetoelectric nanocomposites

The use of polymer based magnetoelectric materials for sensing and actuation applications has been the subject of increasing scientific and technological interest. One of the drawbacks to be overcome in this field is to increase the temperature range of application above 100 ºC. In this way, a nanocomposite material composed by a mixture of two aromatic diamines, 1,3-Bis-2-cyano-3-(3 aminophenoxy)phenoxybenzene (diamine 2CN) and 1,3-Bis(3-aminophenoxy)benzene (diamine 0CN) and CoFe2O4 (CFO) nanoparticles was designed, fabricated and successfully tested for high temperature magnetoelectric applications. Results revealed that CFO nanoparticles are well distributed within the 0CN2CN polymer matrix and that the addition of CFO nanoparticles does not significantly alter the polyimides structure. The magnetization response of the composite is determined by the CFO nanoparticle content. The piezoelectric response of the 0CN2CN polymer matrix (≈11 pC.N-1) and the maximum α33 value (0.8mV.cm-1.Oe-1) are stable over time and decrease only when the composite is subjected to temperatures above 130 ºC. Strategies to further improve the ME response are also discussed.

Energy harvesting performance of BaTiO3/poly(vinylidene fluoride-trifluoroethylene) spin coated nanocomposites

The energy harvesting efficiency of poly(vinylidene fluoride-trifluoroethylene) spin coated films and its nanocomposites with piezoelectric BaTiO3 have been investigated as a function of ceramic filler size and content. It is found that the best energy harvesting performance of ~0.28 W is obtained for the nanocomposite samples with 20% filler content of 10 nm size particles and for 5% filler content for the 100 and 500 nm size fillers. For the larger filler average sizes, the power decreases for filler contents above 5% due to increase of the mechanical stiffness of the samples. Due to the similar dielectric characteristics of the samples, the performance is mainly governed by the mechanical response. The obtained power values, easy processing and the low cost and robustness of the polymer, allow the implementation of the material for micro and nanogenerator applications.

Thin films composed of gold nanoparticles dispersed in a dielectric matrix: the influence of the host matrix on the optical and mechanical responses

Gold nanoparticles were dispersed in two different dielectric matrices, TiO2 and Al2O3, using magnetron sputtering and a post-deposition annealing treatment. The main goal of the present work was to study how the two different host dielectric matrices, and the resulting microstructure evolution (including both the nanoparticles and the host matrix itself) promoted by thermal annealing, influenced the physical properties of the films. In particular, the structure and morphology of the nanocomposites were correlated with the optical response of the thin films, namely their localized surface plasmon resonance (LSPR) characteristics. Furthermore, and in order to scan the future application of the two thin film system in different types of sensors (namely biological ones), their functional behaviour (hardness and Young's modulus change) was also evaluated. Despite the similar Au concentrations in both matrices (~ 11 at.%), very different microstructural features were observed, which were found to depend strongly on the annealing temperature. The main structural differences included: (i) the early crystallization of the TiO2 host matrix, while the Al2O3 one remained amorphous up to 800 °C; (ii) different grain size evolution behaviours with the annealing temperature, namely an almost linear increase for the Au:TiO2 system (from 3 to 11 nm), and the approximately constant values observed in the Au:Al2O3 system (4–5 nm). The results from the nanoparticle size distributions were also found to be quite sensitive to the surrounding matrix, suggesting different mechanisms for the nanoparticle growth (particle migration and coalescence dominating in TiO2 and Ostwald ripening in Al2O3). These different clustering behaviours induced different transmittance-LSPR responses and a good mechanical stability, which opens the possibility for future use of these nanocomposite thin film systems in some envisaged applications (e.g. LSPR-biosensors).

Free-standing multilayered membranes based on graphene and natural polymers for biomedical applications

Dissertação de mestrado integrado em Engenharia Biomédica (área de especialização em Biomateriais, Reabilitação e Biomecânica)

Produção e caracterização de filmes finos nanocompósitos de Au-Ag dispersos numa matriz dielétrica, com efeito de ressonância de plasmão de superfície localizado

Dissertação de mestrado em Engenharia de Materiais