In-situ X-ray diffraction studies during growth of Ni-Ti shape memory alloy films and their complementary ex-situ characterization

Shape Memory Alloy (SMA) Ni-Ti films have attracted much interest as functional and smart materials due to their unique properties. However, there are still important issues unresolved like formation of film texture and its control as well as substrate effects. Thus, the main challenge is not only the control of the microstructure, including stoichiometry and precipitates, but also the identification and control of the preferential orientation since it is a crucial factor in determining the shape memory behaviour. The aim of this PhD thesis is to study the optimisation of the deposition conditions of films of Ni-Ti in order to obtain the material fully crystallized at the end of the deposition, and to establish a clear relationship between the substrates and texture development. In order to achieve this objective, a two-magnetron sputter deposition chamber has been used allowing to heat and to apply a bias voltage to the substrate. It can be mounted into the six-circle diffractometer of the Rossendorf Beamline (ROBL) at the European Synchrotron Radiation Facility (ESRF), Grenoble, France, enabling an in-situ characterization by X-ray diffraction(XRD) of the films during their growth and annealing. The in-situ studies enable us to identify the different steps of the structural evolution during deposition with a set of parameters as well as to evaluate the effect of changing parameters on the structural characteristics of the deposited film. Besides the in-situ studies, other complementary ex-situ characterization techniques such as XRD at a laboratory source, Rutherford backscattering spectroscopy(RBS), Auger electron spectroscopy (AES), cross-sectional transmission electron microscopy (X-TEM), scanning electron microscopy (SEM), and electrical resistivity (ER) measurements during temperature cycling have been used for a fine structural characterization. In this study, mainly naturally and thermally oxidized Si(100) substrates, TiN buffer layers with different thicknesses (i.e. the TiN topmost layer crystallographic orientation is thickness dependent) and MgO(100) single crystals were used as substrates. The chosen experimental procedure led to a controlled composition and preferential orientation of the films. The type of substrate plays an important role for the texture of the sputtered Ni-Ti films and according to the ER results, the distinct crystallographic orientations of the Ni-Ti films influence their phase transformation characteristics.

Effect of different dopant elements on the properties of ZnO thin films

Vacuum, Vol. 64

Design of New Materials for Passive Vibration Control

The objective of this contribution is to extend the models of cellular/composite material design to nonlinear material behaviour and apply them for design of materials for passive vibration control. As a first step a computational tool allowing determination of optimised one-dimensional isolator behaviour was developed. This model can serve as a representation for idealised macroscopic behaviour. Optimal isolator behaviour to a given set of loads is obtained by generic probabilistic metaalgorithm, simulated annealing. Cost functional involves minimization of maximum response amplitude in a set of predefined time intervals and maximization of total energy absorbed in the first loop. Dependence of the global optimum on several combinations of leading parameters of the simulated annealing procedure, like neighbourhood definition and annealing schedule, is also studied and analyzed. Obtained results facilitate the design of elastomeric cellular materials with improved behaviour in terms of dynamic stiffness for passive vibration control.

A study on metallurgy and corrosion of ancient copper-based artefacts from the portuguese territory

Dissertação apresentada para a obtenção do Grau de Doutor em Conservação e Restauro, especialidade Ciências da Conservação, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Modelos geológicos estocásticos 3D e interface para modelos de simulação de fluxo: aplicação à área subjacente da antiga fábrica da SPEL

Dissertação para obtenção do grau de Mestre em Engenharia Geológica (Georrecursos)

Archaeometallurgical study of artefacts from Castro de Vila Nova de São Pedro (Azambuja, Portugal)

Dissertação para obtenção do Grau de Mestre em Conservação e Restauro

Design of New Materials for Passive Vibration Control

The aim of this contribution is to extend the techniques of composite materials design to non-linear material behaviour and apply it for design of new materials for passive vibration control. As a first step a computational tool allowing determination of macroscopic optimized one-dimensional isolator behaviour was developed. Voigt, Maxwell, standard and more complex material models can be implemented. Objective function considers minimization of the initial reaction and/or displacement peak as well as minimization of the steady-state amplitude of reaction and/or displacement. The complex stiffness approach is used to formulate the governing equations in an efficient way. Material stiffness parameters are assumed as non-linear functions of the displacement. The numerical solution is performed in the complex space. The steady-state solution in the complex space is obtained by an iterative process based on the shooting method which imposes the conditions of periodicity with respect to the known value of the period. Extension of the shooting method to the complex space is presented and verified. Non-linear behaviour of material parameters is then optimized by generic probabilistic meta-algorithm, simulated annealing. Dependence of the global optimum on several combinations of leading parameters of the simulated annealing procedure, like neighbourhood definition and annealing schedule, is also studied and analyzed. Procedure is programmed in MATLAB environment.

Archaeometallurgical study of pre and protohistoric production remains and artefacts from Southern Portugal

Dissertação para obtenção do Grau de Doutor em Conservação e Restauro, especialidade Ciências da Conservação

Study and characterization of the ZnPc:C60/MoOx interface in organic solar cells by means of photoelectron spectroscopy

Dissertation to obtain the academic degree of Master in materials engineering submitted to the Faculty of science and engineering of Universidade Nova de Lisboa

Digital microfluidics on paper

This thesis is one of the first reports of digital microfluidics on paper and the first in which the chip’s circuit was screen printed unto the paper. The use of the screen printing technique, being a low cost and fast method for electrodes deposition, makes the all chip processing much more aligned with the low cost choice of paper as a substrate. Functioning chips were developed that were capable of working at as low as 50 V, performing all the digital microfluidics operations: movement, dispensing, merging and splitting of the droplets. Silver ink electrodes were screen printed unto paper substrates, covered by Parylene-C (through vapor deposition) as dielectric and Teflon AF 1600 (through spin coating) as hydrophobic layer. The morphology of different paper substrates, silver inks (with different annealing conditions) and Parylene deposition conditions were studied by optical microscopy, AFM, SEM and 3D profilometry. Resolution tests for the printing process and electrical characterization of the silver electrodes were also made. As a showcase of the applications potential of these chips as a biosensing device, a colorimetric peroxidase detection test was successfully done on chip, using 200 nL to 350 nL droplets dispensed from 1 μL drops.

Field-effect transistors based on Zinc oxide nanoparticles

This work reports the development of field-effect transistors (FETs), whose channel is based on zinc oxide (ZnO) nanoparticles (NPs). Using screen-printing as the primary deposition technique, different inks were developed, where the semiconducting ink is based on a ZnO NPs dispersion in ethyl cellulose (EC). These inks were used to print electrolyte-gated transistors (EGTs) in a staggered-top gate structure on glass substrates, using a lithium-based polymeric electrolyte. In another approach, FETs with a staggered-bottom gate structure on paper were developed using a sol-gel method to functionalize the paper’s surface with ZnO NPs, using zinc acetate dihydrate (ZnC4H6O4·2H2O) and sodium hydroxide (NaOH) as precursors. In this case, the paper itself was used as dielectric. The various layers of the two devices were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared spectroscopy (FTIR), thermogravimetric and differential scanning calorimetric analyses (TG-DSC). Electrochemical impedance spectroscopy (EIS) was used in order to evaluate the electric double-layer (EDL) formation, in the case of the EGTs. The ZnO NPs EGTs present electrical modulation for annealing temperatures equal or superior to 300 ºC and in terms of electrical properties they showed On/Off ratios in the order of 103, saturation mobilities (μSat) of 1.49x10-1 cm2(Vs)-1 and transconductance (gm) of 10-5 S. On the other hand, the ZnO NPs FETs on paper exhibited On/Off ratios in the order of 102, μSat of 4.83x10- 3 cm2(Vs)-1and gm around 10-8 S.

The early metallurgy in Southwestern Iberia: metals from the Chalcolithic Settlement of São Pedro (Redondo)

Archaeological excavations carried out in the archaeological site of São Pedro (Southern Portugal) revealed a Chalcolithic settlement occupied in different moments of the 3rd millennium BC. The material culture recovered includes different types of materials, such as ceramics, lithics and metals. The later comprises about 30 artefacts with different typologies such as tools (e.g. awls, chisels and a saw) and weapons (e.g. daggers and arrowheads) mostly belonging to the 2nd and 3rd quarter of the 3rd millennium BC. In the present work the collection of chalcolithic metallic artefacts recovered in São Pedro was characterized. Analytical studies involved micro energy dispersive X-ray fluorescence spectrometry (micro-EDXRF) to determine elemental composition, together with optical microscopy and Vickers microhardness testing for microstructural characterisation and hardness determination. Main results show copper with variable amounts of arsenic and very low content of other impurities, such as iron. Moreover, nearly half of the collection is composed by arsenical copper alloys (As > 2 wt.%) and an association was found between arsenic content and typology since the weapons group (mostly daggers) present higher values than tools (mostly awls). These results suggest some criteria in the selection of arsenic-rich copper ores or smelting products. Furthermore, after casting an artefact would have been hammered, annealed and sometimes, finished with a hammering operation. Additionally, microstructural variations in this collection reveal somewhat different operational conditions during casting, annealing and forging, as expected in such a primitive metallurgy. Moreover the operational sequence seems to be used to achieve the required shape to the object, rather than to intentionally make the alloy harder. Overall, this study suggests that Chalcolithic metallurgists might have a poor control of the addition of arsenic and/or were unable to use this element to increase the hardness of tools and weapons. Finally, the compositions, manufacturing processes and hardness were compared to those from neighbouring regions and different chronological periods.

Perylene Diimide acceptors: Fabrication and characterization of electron-only, hole-only devices and solar cells

The thrust towards energy conservation and reduced environmental footprint has fueled intensive research for alternative low cost sources of renewable energy. Organic photovoltaic cells (OPVs), with their low fabrication costs, easy processing and flexibility, represent a possible viable alternative. Perylene diimides (PDIs) are promising electron-acceptor candidates for bulk heterojunction (BHJ) OPVs, as they combine higher absorption and stability with tunable material properties, such as solubility and position of the lowest unoccupied molecular orbital (LUMO) level. A prerequisite for trap free electron transport is for the LUMO to be located at a level deeper than 3.7 eV since electron trapping in organic semiconductors is universal and dominated by a trap level located at 3.6 eV. Although the mostly used fullerene acceptors in polymer:fullerene solar cells feature trap-free electron transport, low optical absorption of fullerene derivatives limits maximum attainable efficiency. In this thesis, we try to get a better understanding of the electronic properties of PDIs, with a focus on charge carrier transport characteristics and the effect of different processing conditions such as annealing temperature and top contact (cathode) material. We report on a commercially available PDI and three PDI derivatives as acceptor materials, and its blends with MEH-PPV (Poly[2-methoxy 5-(2-ethylhexyloxy)-1,4-phenylenevinylene]) and P3HT (Poly(3-hexylthiophene-2,5-diyl)) donor materials in single carrier devices (electron-only and hole-only) and in solar cells. Space-charge limited current measurements and modelling of temperature dependent J-V characteristics confirmed that the electron transport is essentially trap-free in such materials. Different blend ratios of P3HT:PDI-1 (1:1) and (1:3) show increase in the device performance with increasing PDI-1 ratio. Furthermore, thermal annealing of the devices have a significant effect in the solar cells that decreases open-circuit voltage (Voc) and fill factor FF, but increases short-circuit current (Jsc) and overall device performance. Morphological studies show that over-aggregation in traditional donor:PDI blend systems is still a big problem, which hinders charge carrier transport and performance in solar cells.