Estudo comparativo de utilização de SER, MIG/MAG e Friction Surfacing na reparação de braços de suspensão de VBTP-M113

Nas últimas décadas Friction Surfacing despertou bastante interesse por permitir revestir metais no estado sólido desenvolvendo-se a temperaturas inferiores às de fusão, evitando assim as afetações que dai advém. No presente trabalho existem dois blocos principais, um primeiro onde se caraterizou o material do braço de suspensão do M113, e um segundo onde se produziram revestimentos recorrendo às três técnicas de revestimento em estudo (FS, Fios Fluxados e SER), com o objetivo de se proceder ao seu estudo e comparação. No processo de caraterização do aço do braço, foram realizados diversos ensaios, dos quais se salientam os ensaios de durezas Vickers e os ensaios de faiscamento, concluindo-se que o aço que mais se assemelha com o do braço é o AISI 4140. Para a caraterização dos revestimentos foram definidos diferentes tipos de ensaios, Metalúrgicos e Mecânicos, com a finalidade principal de abranger uma ampla gama de solicitações semelhantes às que são requeridas ao componente em serviço. Nos ensaios Metalúrgicos foram avaliadas as ligações, a existência de defeitos, as ZTA e as alterações metalográficas. A avaliação das propriedades mecânicas foi obtida através de ensaios de dureza, desgaste, flexão em três pontos e Push-Pull. Da realização destes ensaios verificou-se que os revestimentos obtidos por FS apresentam melhores propriedades, tanto Metalúrgicas como Mecânicas Por fim, foi elaborada uma avaliação dos custos operacionais envolvidos na realização da reparação de um braço de suspensão, concluindo-se que FS, apesar de apresentar os revestimentos com melhores propriedades, é ainda uma tecnologia pouco viável economicamente, fato que se deve á baixa eficiência apresentada.

Today's pupils tomorrow's engineers! Pedagogy and policy:a UK perspective

Purpose – This paper aims to provide a critical analysis of UK Government policy in respect of recent moves to attract young people into engineering. Drawing together UK and EU policy literature, the paper considers why young people fail to look at engineering positively. Design/methodology/approach – Drawing together UK policy, practitioner and academic-related literature the paper critically considers the various factors influencing young people's decision-making processes in respect of entering the engineering profession. A conceptual framework providing a diagrammatic representation of the “push” and “pull” factors impacting young people at pre-university level is given. Findings – The discussion argues that higher education in general has a responsibility to assist young people overcome negative stereotypical views in respect of engineering education. Universities are in the business of building human capability ethically and sustainably. As such they hold a duty of care towards the next generation. From an engineering education perspective, the major challenge is to present a relevant and sustainable learning experience that will equip students with the necessary skills and competencies for a lifelong career in engineering. This may be achieved by promoting transferable skills and competencies or by the introduction of a capabilities-driven curriculum which brings together generic and engineering skills and abilities. Social implications – In identifying the push/pull factors impacting young people's decisions to study engineering, this paper considers why, at a time of global recession, young people should select to study the required subjects of mathematics, science and technology necessary to study for a degree in engineering. The paper identifies the long-term social benefits of increasing the number of young people studying engineering. Originality/value – In bringing together pedagogy and policy within an engineering framework, the paper adds to current debates in engineering education providing a distinctive look at what seems to be a recurring problem – the failure to attract young people into engineering.

Using the Involvement Construct to Understand the Motivations of Customers of Casual Dining Restaurants in the USA

The purpose of this study was to investigate the motivations that push consumers to dine out and restaurant attributes that pull diners to a specific restaurant. Surveys were administered to a convenience sample of 559 respondents at a large university in the Southwest of the USA. Crosstabs, ANOVA, Correlations, Factor Analysis and Multiple Regression were employed to explore differences and relationships between variables. Findings identified a profile of diners at casual restaurants. Using the involvement construct, the push-pull motivational framework, and the hedonic and utilitarian motivational framework, results of this study indicate two primary reasons behind the decision to dine out at casual restaurants and six principal attributes that draw customers into these types of restaurants. In addition, diners were categorized into high/medium/low involvement categories and the linkages between involvement levels and motivations were explored. Both hedonic and utilitarian motivations were identified. Furthermore, motivational factors and restaurant attributes were found to predict diner loyalty. This paper provides the restaurant industry with insight and understanding as to what attracts diners into an establishment and what influences decisions behind dining out.

Understanding catalytic reactions over zeolites: A density functional theory study of selective catalytic reduction of NOX by NH3 over Cu-SAPO-34

Metal exchanged CHA-type (SAPO-34 and SSZ-13) zeolites are promising catalysts for selective catalytic reduction (SCR) of NOx by NH3. However, the understanding of the process at the molecular level is still limited, which hinders the identification of its mechanism and the design of more efficient zeolite catalysts. In this work, modelling the reaction over Cu-SAPO-34, a periodic density functional theory (DFT) study of NH3-SCR was performed using hybrid functional with the consideration of van der Waals (vdW) interactions. A mechanism with a low N–N coupling barrier is proposed to account for the activation of NO. The redox cycle of Cu2+ and Cu+, which is crucial for the SCR process, is identified with detailed analyses. Besides, the decomposition of NH2NO is shown to readily occur on the Brønsted acid site by a hydrogen push-pull mechanism, confirming the collective efforts of Brønsted acid and Lewis acid (Cu2+) sites. The special electronic and structural properties of Cu-SAPO-34 are demonstrated to play an essential role the reaction, which may have a general implication on the understanding of zeolite catalysis.

Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Synthesis of novel organic semiconductors for optoelectronic devices

This thesis describes the synthesis and characterisation of novel conjugated organic materials with optoelectronic application. The first chapter provides an introduction about organic semiconductors and in particular about their working principle from a physical and chemical point of view. An overview of the most common types of solar cells is provided, including examples of some of the best performing materials. The second chapter describes the synthesis of a new library of flavin derivatives as potential active materials for optoelectronic applications. Flavins are natural redox-active molecules, which show potential application in optoelectronics, thanks to their stability and versatility. FPF-Flavins, for instance, could be used either as acceptor units in push-pull polyconjugated systems or as acceptor unit in dyes for DSSCs. In the same chapter a first attempt of synthesising bis-flavins to be used as N-type semiconductors in BHJ devices is described. The third chapter describes the successful synthesis and characterization of a series of conjugated organic molecules based on the benzothiadiazole moiety. Among these, three molecules containing ferrocene as donor unit were tested as sensitizers for DSSCs, reporting a PCE of 0.3% as the best result. Further studies indicated a significant problem of charge recombination which limits the performance. A near-infrared absorbing push-pull polymer, based on BbT as acceptor unit, was also synthesised and tested in BHJ devices as P-type semiconductor in blend with PC71BM, showing a VOC of 0.71 V. Finally, the last chapter describes the synthesis of several tetrathiafulvalene derivatives in order to explore this moiety as donor unit in dyes for DSSCs and as HTM for perovskite-based solar cells. In particular, two very simple dyes were synthesised and implemented in DSSCs reporting a PCE 0.2% and 0.4%, respectively. The low efficiency was associated to the tendency to aggregate at the solid state, with the absorption shifting from the visible to the infrared range. A conjugated molecule, containing a DPP core, was also synthesised and tested as HTM for perovskite solar cells. The best reported PCE of 7.7% was obtained without any additives. A case study about dehalogenation and “halogen dance” in TTF iodide is also presented.

Diversidade da entomofauna em milho consorciado com sorgo e crotalária em diferentes arranjos.

2016

Sintesi, caratterizzazione e nano-strutturazione di politiofeni e loro applicazione in celle solari

Negli ultimi decenni i polimeri coniugati, grazie alla loro peculiarità di essere dei semiconduttori organici, hanno attirato l’attenzione della ricerca scientifica, e tra questi composti rientrano i politiofeni. Versatilità, robustezza chimica strutturale e fluorescenza sono alcune delle proprietà che caratterizzano tali composti e che hanno permesso di esplorare nuovi materiali da un punto di vista scientifico e tecnologico. Recentemente molto interessanti sono risultate essere le nanoparticelle politiofeniche poiché permettono di modulare le proprietà chimico-fisiche dei relativi polimeri, ampliandone le potenzialità a trovare applicazione in molteplici dispositivi elettronici, tra cui le celle solari (CS) organiche. Infatti, molto attivo è l’interesse della comunità scientifica per ottimizzare questi dispositivi ricercando nuovi prodotti che soddisfino diversi requisiti, come riduzione dell’impatto ambientale, la facilità di preparazione e compatibilità con substrati flessibili. In tale contesto, uno degli obiettivi della ricerca attualmente si focalizza sulla preparazione di nuovi accettori da usare in CS organiche alternativi ai derivati fullerenici, i quali presentano diversi svantaggi. Alla luce dei più recenti risultati si è visto che i politiofeni push-pull, caratterizzati dall’alternanza di gruppi accettori (A) e gruppi donatori (D), hanno una notevole potenzialità a rimpiazzare tali materiali e ad essere usati come accettori non-fullerenici. Infatti, questi hanno permesso di ottenere buoni risultati in termini di conversioni ed efficienze delle celle fotovoltaiche. Lo scopo di questo lavoro di tesi è sintetizzare sei nuovi polimeri a base tiofenica (quattro con sequenza A-D e due con sequenza A-A) per studiarne le possibili applicazioni come materiali accettori non-fullerenici e la loro organizzazione in strutture ordinate di nanoparticelle.

Development of a novel heat treatment for high performances L-PBF Ti6Al4V alloy: microstructural and mechanical characterization

This work presents the experimental development of a novel heat treatment for a high performance Laser Powder Bed Fusion Ti6Al4V alloy. Additive manufacturing production processes for titanium alloys are particularly of interest in cutting-edge engineering fields, however, high frequency laser induced thermal cycles generate a brittle as built microstructure. For this reason, heat treatments compliant with near net shape components are needed before their homologation and usage. The experimental campaign focused on the development of a multi-step heat treatment leading to a bilamellar microstructure. In fact, according to literature, such a microstructure should be promising in terms of mechanical properties both under static and cyclic loads. The heat treatment development has asked for the preliminary analyses of samples annealed and aged in laboratory, implementing several cycles, differing for what concerns temperatures, times and cooling rates. Such a characterization has been carried out through optical and electron microscopy analyses, image analyses, hardness and tensile tests. As a result, the most suitable thermal cycle has been selected and performed using industrial equipment on mini bending fatigue samples with different surface conditions. The same tests have been performed on a batch of traditionally treated samples, to provide with a comparison. This master thesis activity has finally led to the definition of a heat treatment resulting into a bilamellar microstructure, promising in terms of fatigue performances with respect to the traditionally treated alloy ones. The industrial implementation of such a heat treatment will require further improvements, particularly for what concerns the post annealing water quench, in order to prevent any surface alteration potentially responsible for the fatigue performances drop. Further development of the research may also include push-pull fatigue tests, crack grow propagation and residual stresses analyses.

Sintesi e caratterizzazione di polimeri per l’ottica non lineare

L'osservazione di diversi fenomeni ottici come la generazione della seconda o della terza armonica (generazione di luce con frequenza raddoppiata (SHG) o generazione di luce con frequenza triplicata (THG)) quando un materiale interagisce con una sorgente ad alta intensità, ha portato ad un crescente interesse per le proprietà ottiche non lineari (NLO). Questi ed altri fenomeni ottici non lineari potrebbero essere impiegati per aumentare le prestazioni dei dispositivi optoelettronici e fornire soluzioni per progettare nuovi metamateriali funzionali. L'impiego di sistemi polimerici contenenti gruppi funzionali con caratteristiche NLO rappresenta una sfida per migliorare tali proprietà e la loro lavorabilità. In questo lavoro, è stata sviluppata una strategia sintetica per ottenere un cromoforo con struttura donatore-accettore-donatore (D-A-D), dove la simmetria dei dipoli (push-pull-push) può potenzialmente fornire proprietà NLO del terzo ordine. Attraverso una sintesi multistep è stato sintetizzato il monomero a base metacrilica con il cromoforo NLO, successivamente copolimerizzato con lo stirene per aumentare la lavorabilità del polimero. Il polimero ed il monomero saranno impiegati per preparare cristalli fotonici. Inoltre, verrà effettuata un'ampia caratterizzazione per approfondire le proprietà ottiche e quindi per ottimizzare i dispositivi finali.

Travel preferences of the residents of Guimarães: a revised model of push and pull motives

The historic center of the Portuguese city of Guimarães is a world heritage site (UNESCO) since 2001, having hosted the European Capital of Culture (ECOC) in 2012. In this sense, Guimarães has made a major effort in promoting tourism, positioning itself as an urban and cultural tourism destination. The present paper has two objectives. The first, to examine if an existing push and pull motivation model finds statistical support with regard to the population of the municipality of Guimarães, a cultural tourism destination. The second, to study the role that important socio-demographic variables, such as gender, age, and education, play in determining travel motivations of residents from this municipality. Insight on tourism motivation may be an important policy tool for tourism planners and managers in the development of products and marketing strategies. The empirical analysis is undertaken based on questionnaires administered in 2012 to residents of Guimarães. The present study shows that gender, age and education make a difference with regard to travel motivations.

Push and Pull Motivations for Quitting: A three-wave investigation of predictors and consequences of turnover

We report a new analysis of data from a multi-year study, some of which were previously published in the current journal. A longitudinal sample of 380 computer specialists was followed over two years, yielding three measures each of job satisfaction, organizational commitment, and turnover intentions, as well as actual turnover, and reasons for leaving, at Times 2 and 3. Career paths were more diverse than the classical distinction between stayers and leavers implies. Furthermore, although the largest single group of leavers cited “push” reasons, conforming to the classical withdrawal model, a sizable number were attracted to another job (“pull motivation”). In a three-wave structural equation model, job (dis)satisfaction predicted turnover, while organizational commitment exerted its influence only via its association with job satisfaction. As expected, however, attitudes predicted turnover only for participants with push motivation. Quitting, in turn, predicted an improvement in both satisfaction and commitment, indicating that it paid off for the individual. The necessity to study consequences of turnover and to distinguish between different subgroups of stayers and leavers is emphasized.

Qualitative and quantitative formal model-based safety analysis : push the safety button

Magdeburg, Univ., Fak. für Informatik, Diss., 2011

An agency-oriented model to explain vine-growing specialization in the province of Barcelona (Catalonia, Spain) in the mid-nineteenth century

[cat] En aquest treball presentem un model per explicar el procés d’especialització vitícola assolit als municipis de la província de Barcelona, a mitjans del s. XIX,que cerca entendre com va sorgir històricament un avantatge comparatiu fruit d’un procés que esdevindria un dels punts de partida del procés d’industrialització a Catalunya. Els resultats confirmen els papers jugats pel impuls “Boserupià” de la població en un context d’intensificació de l’ús de la terra, i d’un impuls del mercat “Smithià” en un context d’expansió de la demanda per part de les economies atlàntiques. També es posa de manifest la importància de les dotacions agro-ecològiques i les condicions socioinstitucionals relacionades amb la desigualtat d’ingrés. La difusió de la vinya donà com a resultat unes comunitats rurals menys desiguals fins al 1820, tot i que aquesta desigualtat augmentà de nou a partir d'aleshores.