Thermal conditions affecting heat transfer in FDM/FFE: a contribution towards the numerical modelling of the process

The performance of parts produced by Free Form Extrusion (FFE), an increasingly popular additive manufacturing technique, depends mainly on their dimensional accuracy, surface quality and mechanical performance. These attributes are strongly influenced by the evolution of the filament temperature and deformation during deposition and solidification. Consequently, the availability of adequate process modelling software would offer a powerful tool to support efficient process set-up and optimisation. This work examines the contribution to the overall heat transfer of various thermal phenomena developing during the manufacturing sequence, including convection and radiation with the environment, conduction with support and between adjacent filaments, radiation between adjacent filaments and convection with entrapped air. The magnitude of the mechanical deformation is also studied. Once this exercise is completed, it is possible to select the material properties, process variables and thermal phenomena that should be taken in for effective numerical modelling of FFE.

Surface plasmon resonance-coupled photoluminescence and resistive switching behavior of pulsed laser-deposited Ag:SiC nanocermet thin films

In this study, Ag:SiC nanocermets were prepared via rapid thermal annealing (RTA) of pulsed laser-deposited SiC/Ag/SiC trilayers grown on Si substrate. Atomic force microscope images show that silver nanoparticles (Ag NPs) are formed after RTA, and the size of NPs increases with increasing Ag deposition time (t Ag). Sharp dip observed in the reflectance spectra confirmed the existence of Ag surface plasmons (SPs). The infrared transmission spectra showed an intense and broad absorption band around 780–800 cm−1 that can be assigned to Si-C stretching vibration mode. Influence of t Ag on the spectral characteristics of SP-enhanced photoluminescence (PL) and electrical properties of silicon carbide (SiC) films has been investigated. The maximum PL enhancement by 5.5 times for Ag:SiC nanocermets is achieved when t Ag ≈ 50 s. This enhancement is due to the strong resonant coupling between SiC and the SP oscillations of the Ag NPs. Presence of Ag NPs in SiC also induces a forming-free resistive switching with switching ratio of 2 × 10−2. The analysis of I–V curves demonstrates that the trap-controlled space-charge-limited conduction with filamentary model is the governing mechanism for the resistive switching in nanocerment thin films.

Effect of annealing temperature on photoluminescence and resistive switching characteristics of ZnO/Al2O3 multilayer nanostructures

This work demonstrates the role of defects generated during rapid thermal annealing of pulsed laser deposited ZnO/Al2O3 multilayer nanostructures in presence of vacuum at different temperatures (Ta) (500–900 C) on their electrical conductance and optical characteristics. Photoluminescence (PL) emissions show the stronger green emission at Ta 600 C and violet–blue emission at TaP800 C, and are attributed to oxygen vacancies and zinc related defects (zinc vacancies and interstitials) respectively. Current–voltage (I–V) characteristics of nanostructures with rich oxygen vacancies and zinc related defects display the electroforming free resistive switching (RS) characteristics. Nanostructures with rich oxygen vacancies exhibit conventional and stable RS behavior with high and low resistance states (HRS/LRS) ratio 104 during the retention test. Besides, the dominant conduction mechanism of HRS and LRS is explained by trap-controlled-space-charge limited conduction mechanism, where the oxygen vacancies act as traps. On the other hand, nanostructures with rich zinc related defects show a diode-like RS behavior. The rectifying ratio is found to be sensitive on the zinc interstitials concentration. It is assumed that the rectifying behavior is due to the electrically formed interface layer ZnAl2O4 at the Zn defects rich ZnO crystals – Al2O3 x interface and the switching behavior is attributed to the electron trapping/de-trapping process at zinc vacancies.

Dielectric relaxation dynamics of high-temperature piezoelectric polyimide copolymers

Polyimide co-polymers have been prepared based on different diamines as co-monomers: a diamine without CN groups and a novel synthesized diamine with two CN groups prepared by polycondensation reaction followed by thermal cyclodehydration. Dielectric spectroscopy measurements were performed and the dielectric complex function, ac conductivity and electric modulus of the co-polymers were investigated as a function of CN group content in the frequency range from 0.1 Hz to 107 Hz at temperatures from 25 to 260 °C. For all samples and temperatures above 150ºC, the dielectric constant increases with increasing temperature due to increaseing conductivity. The α-relaxation is just detected for the sample without CN groups, being this relaxation overlapped by the electrical conductivity contributions in the remaining samples. For the copolymer samples and the polymer with CN groups an important Maxwell-Wagner-Sillars contribution is detected. The mechanisms responsible for the dielectric relaxation, conduction process and electric modulus response have been discussed as a function of the CN groups content present in the samples.

Electrically tunable resonant scattering in fluorinated bilayer graphene

Adatom-decorated graphene offers a promising new path towards spintronics in the ultrathin limit. We combine experiment and theory to investigate the electronic properties of dilutely fluorinated bilayer graphene, where the fluorine adatoms covalently bond to the top graphene layer. We show that fluorine adatoms give rise to resonant impurity states near the charge neutrality point of the bilayer, leading to strong scattering of charge carriers and hopping conduction inside a field-induced band gap. Remarkably, the application of an electric field across the layers is shown to tune the resonant scattering amplitude from fluorine adatoms by nearly twofold. The experimental observations are well explained by a theoretical analysis combining Boltzmann transport equations and fully quantum-mechanical methods. This paradigm can be generalized to many bilayer graphene-adatom materials, and we envision that the realization of electrically tunable resonance may be a key advantage in graphene-based spintronic devices.

Cultura, liderança e resultados escolares: uma abordagem a partir das representações dos alunos do ensino secundário

Grande parte dos estudos produzidos sobre a liderança escolar tem incidido na análise da relação entre os processos de liderança, a aprendizagem e o sucesso. Embora esta convergência de enfoque (liderança/sucesso) encubra abordagens teóricas, disciplinares e metodológicas muito diferenciadas, é evidente a presença de uma perspetiva unidirecional, mais focada nas políticas e nas práticas de liderança e menos na forma como estas são entendidas pelos alunos. Neste artigo, propomos um enfoque invertido, focado nas representações dos alunos sobre os processos de liderança. Do ponto de vista metodológico, recorremos aos dados recolhidos no âmbito de quatro estudos de caso realizados em escolas/agrupamentos com ensino secundário, resultantes da administração de um inquérito por questionário e da realização de focus group a alunos com resultados académicos de excelência e a alunos não incluídos neste nível de desempenho. Elegemos como referência analítica um estudo de caso de longa duração, a partir do qual colocamos em confronto os dados recolhidos nos outros três contextos estudados. Os resultados deste estudo apontam para a existência de relações e diferenças significativas entre a cultura organizacional da escola e os estilos de liderança, sendo destacada a importância do papel do Diretor na condução do ideário de excelência da escola.

Enhanced resistive switching and multilevel behavior in bilayered HfAlO/HfAlOx structures for non-volatile memory applications

In this work, hafnium aluminum oxide (HfAlO) thin films were deposited by ion beam sputtering deposition technique on Si substrate. The presence of oxygen vacancies in the HfAlOx layer deposited in oxygen deficient environment is evidenced from the photoluminescence spectra. Furthermore, HfAlO(oxygen rich)/HfAlOx(oxygen poor) bilayer structures exhibit multilevel resistive switching (RS), and the switching ratio becomes more prominent with increasing the HfAlO layer thickness. The bilayer structure with HfAlO/HfAlOx thickness of 30/40 nm displays the enhanced multilevel resistive switching characteristics, where the high resistance state/ intermediate resistance state (IRS) and IRS/low resistance state resistance ratios are 102 and 5 105 , respectively. The switching mechanisms in the bilayer structures were investigated by the temperature dependence of the three resistance states. This study revealed that the multilevel RS is attributed to the coupling of ionic conduction and the metallic conduction, being the first associated to the formation and rupture of conductive filaments related to oxygen vacancies and the second with the formation of a metallic filament. Moreover, the bilayer structures exhibit good endurance and stability in time.

Electronic structure and optical signatures of semiconducting transition metal dichalcogenide nanosheets

CONSPECTUS: Two-dimensional (2D) crystals derived from transition metal dichalcogenides (TMDs) are intriguing materials that offer a unique platform to study fundamental physical phenomena as well as to explore development of novel devices. Semiconducting group 6 TMDs such as MoS2 and WSe2 are known for their large optical absorption coefficient and their potential for high efficiency photovoltaics and photodetectors. Monolayer sheets of these compounds are flexible, stretchable, and soft semiconductors with a direct band gap in contrast to their well-known bulk crystals that are rigid and hard indirect gap semiconductors. Recent intense research has been motivated by the distinct electrical, optical, and mechanical properties of these TMD crystals in the ultimate thickness regime. As a semiconductor with a band gap in the visible to near-IR frequencies, these 2D MX2 materials (M = Mo, W; X = S, Se) exhibit distinct excitonic absorption and emission features. In this Account, we discuss how optical spectroscopy of these materials allows investigation of their electronic properties and the relaxation dynamics of excitons. We first discuss the basic electronic structure of 2D TMDs highlighting the key features of the dispersion relation. With the help of theoretical calculations, we further discuss how photoluminescence energy of direct and indirect excitons provide a guide to understanding the evolution of the electronic structure as a function of the number of layers. We also highlight the behavior of the two competing conduction valleys and their role in the optical processes. Intercalation of group 6 TMDs by alkali metals results in the structural phase transformation with corresponding semiconductor-to-metal transition. Monolayer TMDs obtained by intercalation-assisted exfoliation retains the metastable metallic phase. Mild annealing, however, destabilizes the metastable phase and gradually restores the original semiconducting phase. Interestingly, the semiconducting 2H phase, metallic 1T phase, and a charge-density-wave-like 1T' phase can coexist within a single crystalline monolayer sheet. We further discuss the electronic properties of the restacked films of chemically exfoliated MoS2. Finally, we focus on the strong optical absorption and related exciton relaxation in monolayer and bilayer MX2. Monolayer MX2 absorbs as much as 30% of incident photons in the blue region of the visible light despite being atomically thin. This giant absorption is attributed to nesting of the conduction and valence bands, which leads to diversion of optical conductivity. We describe how the relaxation pathway of excitons depends strongly on the excitation energy. Excitation at the band nesting region is of unique significance because it leads to relaxation of electrons and holes with opposite momentum and spontaneous formation of indirect excitons.

Cognitive functioning and efficacy of cognitive intervention in Multiple Sclerosis

Tese de Doutoramento em Psicologia Clínica / Psicologia

Stress-triggered synaptic malfunction: a gate along the path from depressionto dementia

Tese de Doutoramento em Ciências da Saúde.