Molecular mobility of n-ethylene glycol dimethacrylate glass formers upon free radical polymerization

Quando um líquido evita a cristalização durante o arrefecimento, diz-se que entra no estado sobrearrefecido. Se a temperatura continuar a diminuir, o consequente aumento da viscosidade reflecte-se na mobilidade molecular de tal maneira que os tempos característicos se tornam da mesma ordem de grandeza que os tempos acessíveis experimentalmente. Se o arrefecimento continuar, o líquido altamente viscoso acaba por vitrificar, i.e. entra no estado vítreo onde apenas os movimentos locais são permitidos. Os monómeros da família n -etileno glicol dimetacrilato ( n -EGDMA, para n = 1 até 4, que constituem o objecto deste estudo, facilmente evitam a cristalização, sendo pois bons candidatos para estudar a mobilidade molecular nos estados sobrearrefecido e vítreo. A Espectroscopia de Relaxação Dieléctrica (DRS) foi a técnica escolhida para obter informação detalhada sobre a sua dinâmica molecular (Capítulos 1 e 2). A primeira parte deste trabalho consistiu na caracterização dieléctrica dos processos de relaxação existentes acima e abaixo da temperatura de transição vítrea (g T ), a qual aumenta com o aumento do peso molecular (w M ), sendo este resultado confirmado por Calorimetria Diferencial de Varrimento (DSC). No que respeita ao processo cooperativo a , associado à transição vítrea, e ao processo secundário b, observa-se uma dependência com w M , enquanto que o outro processo secundário, g , aparenta ser independente deste factor (Capítulo 3). Nos capítulos seguintes, foram levadas a cabo diferentes estratégias com o objectivo de clarificar os mecanismos que estão na origem destas duas relaxações secundárias (b e g ), assim como conhecer a sua respectiva relação com a relaxação principal (a ). Do estudo, em tempo real, da polimerização isotérmica via radicais livres do TrEGDMA por Calorimetria de Varrimento Diferencial com Modulação de Temperatura (TMDSC), levado a cabo a temperaturas abaixo da g T do polímero final, concluem-se entre outros, dois importantes aspectos: i) que a vitrificação do polímero em formação conduz a graus de conversão relativamente baixos, e ii) que o monómero que está por reagir é expulso da rede polimérica que se forma, dando lugar a uma clara separação de fases (Capítulo 4). Com base nesta informação, o passo seguinte foi estudar separadamente a polimerização isotérmica do di-, tri- e tetra-EGDMA, dando especial atenção às alterações de mobilidade do monómero ainda por reagir. Com as restrições impostas pela formação de ligações químicas, as relaxações a e b detectadas no monómero tendem a desaparecer no novo polímero formado, enquanto que a relaxação g se mantém quase inalterada. Os diferentes comportamentos que aparecem durante a polimerização permitiram a atribuição da origem molecular dos processos secundários: o processo g foi associado ao movimento twisting das unidades etileno glicol, enquanto que a rotação dos grupos carboxilo foi relacionada com a relaxação b (Capítulo 5). No que respeita ao próprio polímero, um processo de relaxação adicional foi detectado, pol b , no poly-DEGDMA, poly-TrEGDMA e poly-TeEGDMA, com características similares ao encontrado nos poli(metacrilato de n -alquilo). Este processo foi confirmado e bem caracterizado aquando do estudo da copolimerização do TrEGDMA com acrilato de metilo (MA) para diferentes composições (Capítulo 6). Para finalizar, o EGDMA, o elemento mais pequeno da família de monómeros estudada, além de vitrificar apresenta uma marcada tendência para cristalizar quer a partir do estado líquido ou do estado vítreo. Durante a cristalização, a formação de uma fase rígida afecta principalmente o processo a , cuja intensidade diminui sem no entanto se observarem modificações significativas na dependência do tempo de relaxação característico com a temperatura. Por outro lado, o processo secundário b torna-se melhor definido e mais estreito, o que pode ser interpretado em termos de uma maior homogeneidade dos micro-ambientes associados aos movimentos locais(Capítulo 7).

Occupational Musculoskeletal Disorders in Europe: Impact, Risk factors and Preventive Regulations

The aim of this article is to characterize musculoskeletal disorders (MSDs) in EU working population according to available Eurostat data, to identify relevant risk factors and to refer existing legislation and standards to prevent MSDs. The following questions will be answered: How often do MSDs occur in EU? What are the risk factors? Do legislation and standards exist to prevent these disorders?

The transformation of work? A quantitative evaluation of changes in work in Portugal

This report is made for the Work Package 15 of WORKS project and tries to develop more information on the Portuguese situation in the work structures changes in the recent years. It starts with an analysis of socio- economical indicators (Macro economical indicators, Employment indicators, Consumption, Technology at the workplace, Productivity), and then approaches the situation in terms of work flexibility in its dimensions of time use and New forms of work organisation. It traces employment in business functions with a sectoral and occupational approach, and analyses the occupational change in South Europe with particular relevance to Portugal (skill utilisation and job satisfaction, occupational and industrial mobility, quantitative evaluation of the shape of employment in Europe. Finaly are analysed the globalisation indicators.

Futures of automobile industry and challenges on sustainable development and mobility

Portugal had only very few foresight exercises on the automobile sector, and the most recent one was a survey held in a project on work organisation systems in the automobile industry, its recent historical paths and the special strategies of location of companies (the WorTiS project). This involved several teams with different disciplinary backgrounds and from two Portuguese universities. The provisional main results of the first round of a Delphi survey held in Portugal on the automotive sector were already published, but a further analysis was not yet done. This foresight survey was done under the WorTiS project, developed in 2004 by IET – Research Centre on Enterprise and Work Innovation (at FCT-UNL), and financed by the Portuguese Ministry of Science and Technology. Some of this experience on foresight analysis is also been transferred to other projects, namely the WORKS project on work organisation restructuring in the knowledge society that received the support from EC and still is running. The majority of experts considered having an average of less knowledge in almost all the scenario topics presented. This means that information on the automotive industry is not spread enough among academics or experts in related fields (regional scientists, innovation economists, engineers, sociologists). Some have a good knowledge but in very specialised fields. Others have expertise on foresight, or macroeconomics, or management sciences, but feel insecure on issues related with futures of automobile sector. Nevertheless, we considered specially the topics where the experts considered themselves to have some knowledge. There were no “irrelevant” topics considered as such by the expert panel. There are also no topics that are not considered a need for co-operation. The lack of technological infrastructures was not considered as a hindered factor for the accomplishment of any scenario. The experts’ panel considered no other international competence besides US, Japan or Germany in these topics. Special focus will be made in this paper on the topic 2. Public policy and automobile industries, and more specifically on the technological and/or research policies issues, where one can specify the automobile’s role in transport policies with further implications like environment, safety, energy, mobility.

Influence of constraining and confinement in the molecular mobility of low molecular weight materials

Dissertation presented to obtain a Ph.D. Degree in Chemical Physics

Service-oriented mobility of java code in web services-based architectures

Dissertação apresentada na Faculdade de Ciências e Tecnologias da Universidade Nova de Lisboa para a obtenção do Grau de Mestre em Engenharia Informática

Liquid crystal mobility and PDLC memory effects

Dissertation presented at Faculdade de Ciências e Tecnologia of Universidade Nova de Lisboa to obtain the Degree of Master in Chemical and Biochemical Engineering

Genotoxic effects in occupational exposure to formaldehyde: A study in anatomy and pathology laboratories and formaldehyde-resins production

ABSTRACT – Background: According to the Report on Carcinogens, formaldehyde ranks 25th in the overall U.S. chemical production, with more than 5 million tons produced each year. Given its economic importance and widespread use, many people are exposed to formaldehyde environmentally and/or occupationally. Presently, the International Agency for Research on Cancer classifies formaldehyde as carcinogenic to humans (Group 1), based on sufficient evidence in humans and in experimental animals. Manyfold in vitro studies clearly indicated that formaldehyde can induce genotoxic effects in proliferating cultured mammalian cells. Furthermore, some in vivo studies have found changes in epithelial cells and in peripheral blood lymphocytes related to formaldehyde exposure. Methods: A study was carried out in Portugal, using 80 workers occupationally exposed to formaldehyde vapours: 30 workers from formaldehyde and formaldehyde-based resins production factory and 50 from 10 pathology and anatomy laboratories. A control group of 85 non-exposed subjects was considered. Exposure assessment was performed by applying simultaneously two techniques of air monitoring: NIOSH Method 2541 and Photo Ionization Detection equipment with simultaneously video recording. Evaluation of genotoxic effects was performed by application of micronucleus test in exfoliated epithelial cells from buccal mucosa and peripheral blood lymphocytes. Results: Time-weighted average concentrations not exceeded the reference value (0.75 ppm) in the two occupational settings studied. Ceiling concentrations, on the other hand, were higher than reference value (0.3 ppm) in both. The frequency of micronucleus in peripheral blood lymphocytes and in epithelial cells was significantly higher in both exposed groups than in the control group (p < 0.001). Moreover, the frequency of micronucleus in peripheral blood lymphocytes was significantly higher in the laboratories group than in the factory workers (p < 0.05). A moderate positive correlation was found between duration of occupational exposure to formaldehyde (years of exposure) and micronucleus frequency in peripheral blood lymphocytes (r = 0.401; p < 0.001) and in epithelial cells (r = 0.209; p < 0.01). Conclusions: The population studied is exposed to high peak concentrations of formaldehyde with a long-term exposure. These two aspects, cumulatively, can be the cause of the observed genotoxic endpoint effects. The association of these cytogenetic effects with formaldehyde exposure gives important information to risk assessment process and may also be used to assess health risks for exposed worker

Strategic analysis on urban mobility

A Work Project, presented as part of the requirements for the Award of a Masters Degree in Management from the NOVA – School of Business and Economics

The new mobility paradigm: transformation of value chain and business models

We would like to thank Philipp Schwarz and Julia Gückel for their dedicated support in preparing this paper and our colleagues and students of the School of Engineering and the Business School for our fruitful discussions.

Automated Generation of Indoor Accessibility Information for Mobility-Impaired Individuals

Dissertation submitted in partial fulfillment of the requirements for the Degree of Master of Science in Geospatial Technologies.

Haptic robot-environment interaction for self-supervised learning in ground mobility

Dissertação para obtenção do Grau de Mestre em Engenharia Eletrotécnica e de Computadores

Technology transition towards electric mobility - technology assessment as a tool for policy design

Paper presented at the Colloquium Gerpisa 2013, Paris (http://gerpisa.org/node/2085), Session n°: 19 New kinds of mobility: old and new business models

Application of geographic information system and modelling in health impact assessment for urban road mobility in Vietnam

Transport is an essential sector in modern societies. It connects economic sectors and industries. Next to its contribution to economic development and social interconnection, it also causes adverse impacts on the environment and results in health hazards. Transport is a major source of ground air pollution, especially in urban areas, and therefore contributing to the health problems, such as cardiovascular and respiratory diseases, cancer, and physical injuries. This thesis presents the results of a health risk assessment that quantifies the mortality and the diseases associated with particulate matter pollution resulting from urban road transport in Hai Phong City, Vietnam. The focus is on the integration of modelling and GIS approaches in the exposure analysis to increase the accuracy of the assessment and to produce timely and consistent assessment results. The modelling was done to estimate traffic conditions and concentrations of particulate matters based on geo-references data. A simplified health risk assessment was also done for Ha Noi based on monitoring data that allows a comparison of the results between the two cases. The results of the case studies show that health risk assessment based on modelling data can provide a much more detail results and allows assessing health impacts of different mobility development options at micro level. The use of modeling and GIS as a common platform for the integration of different assessments (environmental, health, socio-economic, etc.) provides various strengths, especially in capitalising on the available data stored in different units and forms and allows handling large amount of data. The use of models and GIS in a health risk assessment, from a decision making point of view, can reduce the processing/waiting time while providing a view at different scales: from micro scale (sections of a city) to a macro scale. It also helps visualising the links between air quality and health outcomes which is useful discussing different development options. However, a number of improvements can be made to further advance the integration. An improved integration programme of the data will facilitate the application of integrated models in policy-making. Data on mobility survey, environmental monitoring and measuring must be standardised and legalised. Various traffic models, together with emission and dispersion models, should be tested and more attention should be given to their uncertainty and sensitivity

Pedestrian Priority Zones in the Context of Urban Mobility and Valorization of Public Space

The second half of the XX century was marked by a great increase in the number of people living in cities. Urban agglomerations became poles of attraction for migration flows and these phenomena, coupled with growing car-ownership rates, resulted in the fact that modern transport systems are characterized by large number of users and traffic modes. The necessity to organize these complex systems and to provide space for different traffic modes changed the way cities look. Urban areas had to cope with traffic flows, and as a result nowadays typical street pattern consists of a road for motorized vehicles, a cycle lane (in some cases), pavement for pedestrians, parking and a range of crucial signage to facilitate navigation and make mobility more secure. However, this type of street organization may not be desirable in certain areas, more specifically, in the city centers. Downtown areas have always been places where economic, leisure, social and other types of facilities are concentrated, not surprisingly, they often attract large number of people and this frequently results in traffic jams, air and noise pollution, thus creating unpleasant environment. Besides, excessive traffic signage in central locations can harm the image and perception of a place, this relates in particular to historical centers with architectural heritage.