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

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

Intermetallic layer formation and influence in solder joints reliability

Dissertação de mestrado integrado em Materials Engineering

Evolution of the functional properties of titanium–silver thin films for biomedical applications: Influence of in-vacuum annealing

In this work, the thermal stability of TiAgx thin films, deposited by magnetron sputtering, was evaluated, envisaging their application in biomedical devices, namely as electrodes for biosignal acquisition. Based on the composition and microstructural characterization, a set of four representative TiAgx thin films was selected in order to infer whether they are thermally stable in terms of functional properties. In order to achieve this purpose, the structural and morphological evolution of the films with annealing temperature was correlated with their electrical, mechanical and thermal properties. Two distinct zones were identified and two samples from each zone were extensively analysed. In the first zone (zone I), Ti was the main component (Ti-rich zone) while in the second, zone II, the Ag content was more significant. The selected samples were annealed in vacuum at four different temperatures up to 500 oC. For the samples produced within zone I, small microstructural changes were observed due to the recrystallization of the Ti structure and grain size increment. Also, no significant changes were observed with annealing temperature regarding the f l ’ functional properties, being thermally stable up to 500 oC. For higher Ag contents (zone II) the energy supplied by thermal treatments was sufficient to activate the crystallization of Ti-Ag intermetallic phases. A strong increase of the grain size of these phases was also reported. The structural and morphological organization proved to be determinant for the physical responses of the TiAgx system. The hardness and Y g’s modulus were significantly improved with the formation of the intermetallic phases. The silver addition and annealing treatments also played an important role in the electrical conductivity of the films, which was once again improved by the formation of Ti-Ag phases. The thermal diffusivity of the films was practically unchanged with the heat-treatment. This set of results shows that this intermetallic-like thin film system has good thermal stability up to high temperatures (as high as 500 oC), which in case of the highest Ag content zone is particularly evident for electrical and mechanical properties, showing an important improvement. Hardness increases about three times, while resistivity values become half of those from the lowest Ag contents zone. These set of characteristics are consistent with the targeted applications, namely in terms of biomedical sensing devices.

Rheological characterization of EVA and HDPE polymer modified bitumens under large deformation at 20 º C

Large amplitude oscillatory shear (LAOS) coupled with Fourier transform rheology (FTR) was used for the first time to characterize the large deformation behavior of selected bituminous binders at 20 C. Two polymer modified bitumens (PMB) containing recycled EVA and HDPE and two unmodified bitumens were tested with LAOS-FTR. The LAOS-FTR response of all binders was compared at same frequency, at same Deborah number (by tuning the frequency to the relaxation time of each binder) and at same phase shift angle d (by tuning the frequency to the one corresponding to d = 50 in the SAOS response of each sample). In all the approaches, LAOS-FTR results allowed to differentiate between all the nonlinear mechanical characteristics of the tested binders. All binders show LAOS-FTR patterns reminiscent from colloidal dispersions and emulsions. EVA PMB was less prone to strain-induced microstructural changes when compared to HDPE PMB which showed larger values of nonlinear FTR parameters for the range of shear strains tested in LAOS.

Synthesis and characterization of novel 4H-pyran-4-ylidene indole-based heterocyclic systems for several optical applications

The development of organic materials displaying high two-photon absorption (TPA) has attracted much attention in recent years due to a variety of potential applications in photonics and optoelectronics, such as three-dimensional optical data storage, fluorescence imaging, two-photon microscopy, optical limiting, microfabrication, photodynamic therapy, upconverted lasing, etc. The most frequently employed structural motifs for TPA materials are donor–pi bridge–acceptor (D–pi–A) dipoles, donor–pi bridge–donor (D–pi–D) and acceptor–pi bridge-acceptor (A–pi–A) quadrupoles, octupoles, etc. In this work we present the synthesis and photophysical characterization of quadrupolar heterocyclic systems with potential applications in materials and biological sciences as TPA chromophores. Indole is a versatile building block for the synthesis of heterocyclic systems for several optoelectronic applications (chemosensors, nonlinear optical, OLEDs) due to its photophysical properties and donor electron ability and 4H-pyran-4-ylidene fragment is frequently used for the synthesis of red light-emitting materials. On the other hand, 2-(2,6-dimethyl-4H-pyran-4-ylidene)malononitrile (1) and 1,3-diethyl-dihydro-5-(2,6-dimethyl-4H-pyran-4-ylidene)-2-thiobarbituric (2) units are usually used as strong acceptor moieties for the preparation of π-conjugated systems of the push-pull type. These building blocks were prepared by Knoevenagel condensation of the corresponding ketone precursor with malononitrile or 1,3-diethyl-dihydro-2-thiobarbituric acid. The new quadrupolar 4H-pyran-4-ylidene fluorophores (3) derived from indole were prepared through condensation of 5-methyl-1H-indole-3-carbaldehyde with the acceptor precursors 1 and 2, in the presence of a catalytical amount of piperidine. The new compounds were characterized by the usual spectroscopic techniques (UV-vis., FT-IR and multinuclear NMR - 1H, 13C).

Mechanical characterization of old chestnut beams

The main objective of this work is to evaluate, by non-destructive techniques, seven old Chestnut beams. For that, after the geometric assessment and the detailed visual inspection that allowed to strength grade the beams, a series of non-destructive tests was setup. In a first step, non-destructive bending tests, under the elastic limit, were performed to quantify the modulus of elasticity in bending (MoE) of the seven beams. Then, Resistograph® and Pilodyn® tests were done to assess the superficial decay and to have aclearer idea of the voids dimensions. Then, two beams were tested in bending until failure to evaluate the bending strength. In a second step, end parts were cut from the beams, one per end of the beams, to perform Resistograph®, Pilodyn® and ultrasound tests, to quantify the density of the beams and to extract meso-specimens to be used in tension parallel to the grain tests

Application of acoustic emission technique for bond characterization in FRP-masonry systems

The acoustic emission (AE) technique is used for investigating the interfacial fracture and damage propagation in GFRP-and SRG-strengthened bricks during debonding tests. The bond behavior is investigated through single-lap shear bond tests and the fracture progress during the tests is recorded by means of AE sensors. The fracture progress and active debonding mechanisms are characterized in both specimen types with the aim of AE outputs. Moreover, a clear distinction between the AE outputs of specimens with different failure modes, in both SRG-and GFRP-strengthened specimens, is found which allows characterizing the debonding failure mode based on acoustic emission data.

Tensile creep of a structural epoxy adhesive: experimental and analytical characterization

Epoxy adhesives are nowadays being extensively used in Civil Engineering applications, mostly in the scope of the rehabilitation of reinforced concrete (RC) structures. In this context, epoxy adhesives are used to provide adequate stress transference from fibre reinforced polymers (FRP) to the surrounding concrete substrate. Most recently, the possibility of using prestressed FRPs bonded with these epoxy adhesives is also being explored in order to maximize the potentialities of this strengthening approach. In this context, the understanding of the long term behaviour of the involved materials becomes essential. Even when non-prestressed FRPs are used a certain amount of stress is permanently applied on the adhesive interface during the serviceability conditions of the strengthened structure, and the creep of the adhesive may cause a continuous variation in the deformational response of the element. In this context, this paper presents a study aiming to experimentally characterize the tensile creep behaviour of an epoxy-based adhesive currently used in the strengthening of concrete structures with carbon FRP (CFRP) systems. To analytically describe the tensile creep behaviour, the modified Burgers model was fitted to the experimental creep curves, and the obtained results revealed that this model is capable of predicting with very good accuracy the long term behaviour of this material up to a sustained stress level of 60% of the adhesive’s tensile strength.

Tensile and bond characterization of natural fibers embeeded in inorganic matrices

Innovative composite materials made of continuous fibers embedded in mortar matrices have been recently received attention for externally bonded reinforcement of masonry structures. In this regards, application of natural fibers for strengthening of the repair mortars is attractive due to their low specific weight, sustainability and recycability. This paper presents experimental characterization of tensile and pull-out behavior of natural fibers embedded in two different mortar-based matrices. A lime-based and a geopolymeric-based mortar are used as sustainable and innovative matrices. The obtained experimental results and observations are presented and discussed.

In-line rheo-optical characterization during small-scale polymer processing and compounding

As increasingly more sophisticated materials and products are being developed and times-to-market need to be minimized, it is important to make available fast response characterization tools using small amounts of sample, capable of conveying data on the relationships between rheological response, process-induced material structure and product characteristics. For this purpose, a single / twin-screw mini-extrusion system of modular construction, with well-controlled outputs in the range 30-300 g/h, was coupled to a in- house developed rheo-optical slit die able to measure shear viscosity and normal-stress differences, as well as performing rheo-optical experiments, namely small angle light scattering (SALS) and polarized optical microscopy (POM). In addition, the mini-extruder is equipped with ports that allow sample collection, and the extrudate can be further processed into products to be tested later. Here, we present the concept and experimental set-up [1, 2]. As a typical application, we report on the characterization of the processing of a polymer blend and of the properties of extruded sheets. The morphological evolution of a PS/PMMA industrial blend along the extruder, the flow-induced structures developed and the corresponding rheological characteristics are presented, together with the mechanical and structural characteristics of produced sheets. The application of this experimental tool to other material systems will also be discussed.

In-plane and out-of plane experimental characterization of rc masonry infilled frames

Seismic investigations of typical south European masonry infilled frames were performed by testing two reduced scale specimens: one in the in-plane direction and another in the out-ofplane direction. Information about geometry and reinforcement scheme of those structures constructed in 1980s were obtained by [1]. The specimen to be tested in the in-plane direction was constructed as double leaf masonry while the specimen for testing in the out-of-plane direction is constructed with only its exterior leaf since the recent earthquakes have highlighted the vulnerability of the external leaf of the infills in out-of-plane direction [2]. The tests were performed by applying the pre-defined values of displacements in the in-plane and out-of-plane directions in the control points. For in-plane testing it was done by hydraulic actuator and for out-of-plane testing through the application of an airbag. Input and output air in the airbag was controlled by using a software to apply a specific displacement in the control point of the infill wall. Mid-point of the infill was assumed as a control point for outof- plane testing. Deformation and crack patterns of the infill confirm the formation of two-way arching mechanism of the masonry infill until collapse of the upper horizontal interface between infill and frame which is known as weakest interface due to difficulties in filling the mortar between bricks of last row and upper beam. This results in the crack opening through a welldefined path and the consequent collapse of the infill.

Otimização dos parâmetros de processamento em Laser Melting

Dissertação de mestrado integrado em Engenharia Mecânica