Fracture Toughening and Self-Healing of Composite Laminates by Nanofibrous Mats Interleaving

Composite laminates present important advantages compared to conventional monolithic materials, mainly because for equal stiffness and strength they have a weight up to four times lower. However, due to their ply-by-ply nature, they are susceptible to delamination, whose propagation can bring the structure to a rapid catastrophic failure. In this thesis, in order to increase the service life of composite materials, two different approaches were explored: increase the intrinsic resistance of the material or confer to them the capability of self-repair. The delamination has been hindered through interleaving the composite laminates with polymeric nanofibers, which completed the hierarchical reinforcement scale of the composite. The manufacturing process for the integration of the nanofibrous mat in the laminate was optimized, resulting in an enhancement of mode I fracture toughness up to 250%. The effect of the geometrical dimensions of the nano-reinforcement on the architecture of the micro one (UD and woven laminates) was studied on mode I and II. Moreover, different polymeric materials were employed as nanofibrous reinforcement (Nylon 66 and polyvinylidene fluoride). The nano toughening mechanism was studied by micrograph analysis of the crack path and SEM analysis of the fracture surface. The fatigue behavior to the onset of the delamination and the crack growth rate for woven laminates interleaved with Nylon 66 nanofibers was investigated. Furthermore, the impact behavior of GLARE aluminum-glass epoxy laminates, toughened with Nylon 66 nanofibers was investigated. Finally, the possibility of confer to the composite material the capability of self-repair was explored. An extrinsic self-healing-system, based on core-shell nanofibers filled with a two-component epoxy system, was developed by co-electrospinning technique. The healing potential of the nano vascular system has been proved by microscope electron observation of the healing agent release as result of the vessels rupture and the crosslinking reaction was verified by thermal analysis.

Determination of local density of states in amorphous oxide semiconductors with Kelvin Probe Force Microscopy

Amorphous semiconductors are important materials as they can be deposited by physical deposition techniques on large areas and even on plastic substrates. Therefore, they are crucial for transistors in large active matrices for imaging and transparent wearable electronics. The most widely applied candidate for amorphous thin film transistors production is Indium Gallium Zinc Oxide (IGZO). It is attracting much interest because of its optical transparency, facile processing by sputtering deposition and notable improved charge carrier mobility with respect to hydrogenated amorphous silicon a-Si:H. Degradation of the device and long-term performance issues have been observed if IGZO thin film transistors are subjected to electrical stress, leading to a modification of IGZO channel properties and subthreshold slope. Therefore, it is of great interest to have a reliable and precise method to study the conduction band tail, and the density of states in amorphous semiconductors. The aim of this thesis is to develop a local technique using Kelvin Probe Force Microscopy to study the evolution of IGZO DOS properties. The work is divided into three main parts. First, solutions to the non-linear Poisson-Boltzmann equation of a metal-insulator-semiconductor junction describing the charge accumulation and its relation to DOS properties are elaborated. Second macroscopic techniques such as capacitance voltage (CV) measurements and photocurrent spectroscopy are applied to obtain a non-local estimate of band-tail DOS properties in thin film transistor samples. The third part of my my thesis is dedicated to the KPFM measurements. By fitting the data to the developed numerical model, important parameters describing the amorphous conduction band tail are obtained. The results are in excellent agreement with the macroscopic characterizations. KPFM result is comparable also with non-local optoelectronic characterizations, such as photocurrent spectroscopy.

A marcha: a influência do Gerador de Padrão Central

A marcha é influenciada por um conjunto de factores que resultam da interacção e organização própria de sistemas neurais e mecânicos, entre os quais, da dinâmica músculo-esquelética, da modulação pelos centros nervosos superiores, pela modulação aferente e é, também, assumida como sendo controlada pelo Gerador de Padrão Central (GPC), que se define como um programa central baseado num circuito espinal geneticamente determinado, capaz de produzir um ritmo associado a cada marcha. Apresenta-se como objectivo deste trabalho abordar quais os modelos explicativos para o funcionamento do GPC e qual a evidência científica, que continua a ter muitas divergências.

A marcha: a influência do Gerador de Padrão Central

A marcha é influenciada por um conjunto de factores que resultam da interacção e organização própria de sistemas neurais e mecânicos, entre os quais, da dinâmica músculo-esquelética, da modulação pelos centros nervosos superiores, pela modulação aferente e é, também, assumida como sendo controlada pelo Gerador de Padrão Central (GPC), que se define como um programa central baseado num circuito espinal geneticamente determinado, capaz de produzir um ritmo associado a cada marcha. Apresenta-se como objectivo deste trabalho abordar quais os modelos explicativos para o funcionamento do GPC e qual a evidência científica, que continua a ter muitas divergências.

Parcerias público-privadas em educação: novos arranjos na agenda internacional da educação

A intensificação das dinâmicas da globalização nas últimas décadas tem impulsionado a influência de organizações e redes globais de múltiplos atores que atuam no campo das políticas educacionais. O movimento de desterritorialização do fazer político abre espaço para iniciativas de natureza diversa, tanto do ponto de vista da sua esfera de atuação quanto dos atores envolvidos. No contexto dessas novas articulações, iniciativas marcadas pelo envolvimento do setor privado na educação pública têm se desenvolvido em um arranjo complexo referido como parcerias público-privadas em educação. A presente pesquisa analisa essas parcerias em educação, que surgem em um cenário de transformações no próprio funcionamento e organização dos Estados e nas relações que se estabelecem para além das suas fronteiras. Tendo em vista a complexidade do tema e a fim de investigar como ele se traduz e se desenvolve localmente, três experiências são analisadas com maior profundidade: o Chile, com seu sistema de escolas subvencionadas, os Estados Unidos, com as charter schools e a Holanda, que tem seu sistema educacional historicamente estruturado a partir do conceito de school choice. A partir da análise conceitual sobre as parcerias público-privadas em educação e do aprofundamento da pesquisa nesses casos representativos, esta dissertação busca problematizar esse arranjo nas politicas públicas de educação e evidenciar como o seu desenvolvimento está articulado com instituições e processos que transcendem o enquadramento dos Estados-Nação.

Fazer a ponte para a escola de todos(as)

The purpose of this study is to understand what are the matrix elements in which everyday activities of social author/authors, actor/actors and actress/actresses are embedded, in order to carry out the Escola da Ponte s political and pedagogic process (PPP). Thus, the object of this study is to reflect on an experience developed in a public school supported by the Portuguese State within the scenario of institutions that are committed to building up a school of the people by investing in democratization and community participation in their management process. The methodological course of action was targeted at the presuppositions of qualitative research (WOODS, 1999; BURGESS, 1997; MILLS, 1982; OLIVEIRA, 1998; BOGDAN and BIKLEN, 1994; MACEDO, 2000; CASAL, 1996; GEERTZ, 2000), with data collected from random word association (MACHADO and CARVALHO, 2003), the discourse of the interviewed (KAUFMANN, 1996; SILVA, 2006; 2002), observation notes and documents (ELIAS, 1997). Based on a multiple reference and theoretical framework, the investigation revealed elements that are construed as the raw material and pillars supporting the bridge of a school of the people, as well as the self-organization of the school community which emerges as a dimension that binds together all the elements and brings new arrangements into the school dynamics by moving from the individual to the society (DUPUY, 1990). Along this line, the central argument is that in the short and long run the public school quality does not spring from macro educational policies, nor from ephemeral mass-production programs, projects or governmental policies, but from the intent of the professionals working there in becoming authors and characters in the process of building up and carrying out the PPP. The Project has been conceived in the light of the needs and intentionality of the community whose support comes from the participation and social control held by the students families and the community s power to force to action public administration central agencies aiming at having the State fulfill its responsibilities

Dançando com gatos e passáros: O movimento ecossistêmico da ludopoiese na educação infantil

This study shows the movement of educators ludopoiese ecosystem of the Center for Early Childhood Education Marise Paiva-CEIMAP. We used the metaphorof dance as an opportunity to stimulate scientific creativity. Ecosystem Thought, complex thinking, the theory of autopoiesis and Flow Theory, constituted the main theoretical steps to understand the phenomenon of ludopoiese, from the look of your totalidadem with the following objectives: 1 - Identify and interpret the process of self ludopoiética CEIMAP of Early Childhood Educators in the actions of the play, care for and educate in school life; 2 - Analyze Ecosystem Thought from ludopoiéticos how these processes affect and / or possible changes and transformations in practice humanescenteseducational CEIMAP. The theoretical metodógicos steps to address the proposed objectives are grounded in existential action research part of the appreciation of the complexity of the real, considering the human being a whole dynamic. In this sense the game of sand, recreational experiences, the systematic studies and video training were explored with a view to the transdisciplinary relevance of everyday phenomena. New knowledge acquired in accordance with the directions given indicating the movement of the ecosystem studied ludopoiese educators, involved in four main streams: love, play, care for and raise it from love streamline interdependently. The ludopoiese eachteacher would then be fed by this web generated by love that permeates all other educational activities, nurturing and maintaining a constant creative self-organization of knowledge and know-how to be teachers. Thus, every network that generates andstream lines the system emerges ludopoiético biology of love, the open dialogue and playing in the wishing well to the student, the aesthetic beauty of caring and educating, as a human conditionand relevant as possible to live / live not only in teaching children, but in other educational contexts of teaching and teacher education

Degradação anunciada do trabalho formal na Sadia, em Toledo (PR)

Pós-graduação em Geografia - FCT

Desenvolvimento profissional em um grupo de trabalho: professores de matemática que ensinam por meio de softwares educacionais

Pós-graduação em Educação para a Ciência - FC

Middleware per la gestione di interfacce di comunicazione e di sorgenti di contesto in ambienti wireless eterogenei

The full exploitation of multi-hop multi-path connectivity opportunities offered by heterogeneous wireless interfaces could enable innovative Always Best Served (ABS) deployment scenarios where mobile clients dynamically self-organize to offer/exploit Internet connectivity at best. Only novel middleware solutions based on heterogeneous context information can seamlessly enable this scenario: middleware solutions should i) provide a translucent access to low-level components, to achieve both fully aware and simplified pre-configured interactions, ii) permit to fully exploit communication interface capabilities, i.e., not only getting but also providing connectivity in a peer-to-peer fashion, thus relieving final users and application developers from the burden of directly managing wireless interface heterogeneity, and iii) consider user mobility as crucial context information evaluating at provision time the suitability of available Internet points of access differently when the mobile client is still or in motion. The novelty of this research work resides in three primary points. First of all, it proposes a novel model and taxonomy providing a common vocabulary to easily describe and position solutions in the area of context-aware autonomic management of preferred network opportunities. Secondly, it presents PoSIM, a context-aware middleware for the synergic exploitation and control of heterogeneous positioning systems that facilitates the development and portability of location-based services. PoSIM is translucent, i.e., it can provide application developers with differentiated visibility of data characteristics and control possibilities of available positioning solutions, thus dynamically adapting to application-specific deployment requirements and enabling cross-layer management decisions. Finally, it provides the MMHC solution for the self-organization of multi-hop multi-path heterogeneous connectivity. MMHC considers a limited set of practical indicators on node mobility and wireless network characteristics for a coarsegrained estimation of expected reliability/quality of multi-hop paths available at runtime. In particular, MMHC manages the durability/throughput-aware formation and selection of different multi-hop paths simultaneously. Furthermore, MMHC provides a novel solution based on adaptive buffers, proactively managed based on handover prediction, to support continuous services, especially by pre-fetching multimedia contents to avoid streaming interruptions.

Conjugated semiconducting organic materials for electronic applications

Since conjugated polymers, i.e. polymers with spatially extended pi-bonding system have offered unique physical properties, unobtainable for conventional polymers, significant research efforts directed to better understanding of their chemistry, physics and engineering have been undertaken in the past two and half decades. In this thesis we discuss the synthesis, characterisation and investigation of conjugated semiconducting organic materials for electronic applications. Owing to the versatile properties of metal-organic hybrid materials, there is significant promise that these materials can find use in optical or electronic devices in the future. In addressing this issue, the synthesis of bisthiazol-2-yl-amine (BTA) based polymers is attempted and their metallation is investigated. The focus of this work has been to examine whether the introduction of coordinating metal ions onto the polymer backbone can enhance the conductivity of the material. These studies can provide a basis for understanding the photophysical properties of metal-organic polymers based on BTA. In their neutral (undoped) form conjugated polymers are semiconductors and can be used as active components of plastics electronics such as polymer light-emitting diodes, polymer lasers, photovoltaic cells, field-effect transistors, etc. Toward this goal, it is an objective of the study to synthesize and characterize new classes of luminescent polymeric materials based on anthracene and phenanthrene moieties. A series of materials based on polyphenylenes and poly(phenyleneethynylene)s with 9,10-anthrylene subunits are not only presented but the synthesis and characterization of step-ladder and ladder poly(p-phenylene-alt-anthrylene)s containing 9,10-anthrylene building groups within the main chain are also explored. In a separate work, a series of soluble poly-2,7- and 3,6-phenanthrylenes are synthesized. This can enable us to do a systematic investigation into the optical and electronic properties of PPP-like versus PPV-like. Besides, the self-organization of 3,6-linked macrocyclic triphenanthrylene has been investigated by 2D wide-angle X-ray scattering experiments performed on extruded filaments in solution and in the bulk. Additionally, from the concept that donor-acceptor materials can induce efficient electron transfer, the covalent incorporation of perylene tetracarboxydiimide (PDI) into one block of a poly(2,7-carbazole) (PCz)-based diblock copolymer and 2,5-pyrrole based on push-pull type material are achieved respectively.

Lichtsammler hinter Glas : Stabilisierung und Funktionalisierung des pflanzlichen Hauptlichtsammelkomplexes (LHCII) durch biomineralische Einbettung in Nanopartikel

Der Haupt-Lichtsammelkomplex des Fotosystems II (LHCII) setzt sich aus einem Proteinanteil und nicht-kovalent gebundenen Pigmenten – 8 Chlorophyll a, 6 Chlorophyll b und 4 Carotinoide - zusammen. Er assembliert in vivo zu einem Trimer, in dem die Monomereinheiten ebenfalls nicht-kovalent miteinander wechselwirken. Die ausgesprochen hohe Farbstoffdichte und die Tatsache, dass der Komplex rekombinant hergestellt werden kann, machen den LHCII zu einem interessanten Kandidaten für technische Anwendungen wie einer Farbstoffsolarzelle. Allerdings muss hierzu seine thermische Stabilität drastisch erhöht werden.rnDer Einschluss von Proteinen/Enzymen in Silikat erhöht deren Stabilität gegenüber Hitze signifikant. LHCII sollte als erster rekombinanter Membranproteinkomplex mittels kovalent verbundener, polykationischen Sequenzen in Silikat eingeschlossen werden. Hierzu wurde der Komplex auf zwei Weisen polykationisch modifiziert: Auf Genebene wurde die Sequenz des R5-Peptids in den N-terminalen Bereich des LHCP-Gens eingeführt und ein Protokoll zur Überexpression, Rekonstitution und Trimerisierung etabliert. Außerdem wurde eine kovalente Modifikation des trimeren LHCII mit dem Arginin-reichen Protamin über heterobifunktionelle Crosslinker entwickelt. Beide resultierenden LHCII-Derivate waren in der Lage, Silikat autogen zu fällen. Die Stabilisierung der so in Silikat präzipitierten Komplexe war jedoch deutlich geringer als bei nicht-modifizierten Komplexen, die durch eine Spermin-induzierte Copräzipitation eingeschlossenen wurden. Dabei zeigte sich, dass für den Anteil der eingebauten Komplexe und das Ausmaß an Stabilisierung die Größe und klare partikuläre Struktur des Silikats entscheidend ist. Kleine Partikel mit einem Durchmesser von etwa 20 nm führten zu einem Einbau von rund 75 % der Komplexe, und mehr als 80 % des Energietransfers innerhalb des Komplexes blieben erhalten, wenn für 24 Stunden bei 50°C inkubiert wurde. Nicht in Silikat eingeschlossene Komplexe verloren bei 50°C ihren Komplex-internen Energietransfer binnen weniger Minuten. Es war dabei unerheblich, ob die Partikelgröße durch die Wahl des Puffers und des entsprechenden pH-Wertes, oder aber durch Variation des Spermin-zu-Kieselsäure-Verhältnisses erreicht wurde. Wurden die polykationisch veränderten Komplexe in solchen Copräzipitationen verwendet, so erhöhte sich der Anteil an eingebauten Komplexen auf über 90 %, jedoch wurde nur bei der R5-modifizierten Variante vergleichbare Ausmaße an Stabilisierung erreicht. Ein noch höherer Anteil an Komplexen wurde in das Silikatpellet eingebaut, wenn LHCII kovalent mit Silanolgruppen modifiziert wurde (95 %); jedoch war das Ausmaß der Stabilisierung wiederum geringer als bei einer Copräzipitation. Die analysierten Fällungssysteme waren außerdem in der Lage, Titandioxid zu fällen, wobei der Komplex in dieses eingebaut wurde. Allerdings muss das Stabilisierungspotential hier noch untersucht werden. Innerhalb eines Silikatpräzipitats aggregierten die Komplexe nicht, zeigten aber einen inter-trimeren Energietransfer, der sehr wahrscheinlich auf einem Förster Resonanz Mechanismus basiert. rnDies und das hohe Maß an Stabilisierung eröffnen neue Möglichkeiten, rekombinanten LHCII in technischen Applikationen als Lichtsammelkomponente zu verwenden.rn

La crítica poética como instrumento del proyecto de arquitectura

Vivimos en un tiempo de referencias múltiples, de inquietudes en todos los ámbitos -también en el de la arquitectura-, en el que se trata de superar el peso de la historia; donde los apegos sobran y lo que interesa son las posibilidades que nos depara el presente activo. El papel de la crítica de la arquitectura se cuestiona a diario. Los nuevos media son contenedores en actualización continua y el texto ha sido sustituido inevitablemente por la imagen y la acción. En este contexto, la tesis cuestiona por que el nuevo sentido de la crítica sea el de operador que acompaña al proceso del proyecto arquitectónico. Desde el proyecto, sobre el proyecto, para el proyecto, en el proyecto, hacia el proyecto, con el proyecto. Acometiendo la acción crítica desde la complejidad de lo arquitectónico, sobre la diversidad, para la pluralidad, en lo colectivo, hacia la simultaneidad en la síntesis. Para ello, la tesis se apoya en la noción de poética –como complejidad y síntesis interna- y en cinco sistemas arquitectónicos cuya interacción no puede ignorarse –campo, programa, materia, geometría y morfología- para renovar y actualizar la usabilidad de un método crítico –el método Mirregan-Todorov- que ha obtenido reconocidos resultados; pero cuya pesada estructura limita en gran medida su campo de acción y operativa. En este sentido, no se trata ni de una tesis meramente analítica, ni de determinar unos paradigmas arquitectónicos para este siglo. Esta investigación reformula el papel de la crítica de la arquitectura hoy, y parte del orden –como autoorganización- abierto de la crítica poética para proponer una línea de trabajo sobre la interacción de sistemas arquitectónicos de una manera sinérgica y a disposición del proceso de proyecto. Disposición que lleva, como proposición final, a plantear esta actitud como instrumento docente y pedagógico de la asignatura de proyectos arquitectónicos, ya que posibilita la obtención de una serie de cartografías abiertas reflejo de los múltiples agentes y factores de influencia del presente que propician una visión compleja, pero abordable, del proyecto como totalidad. ABSTRACT We live in a time of multiple references, of concerns in all areas -also in architecture-, which tries to overcome the burden of history. A time where the attachments remain and what matters are the possibilities active present lies. The role of criticism of architecture is questioned daily. New media are continuously updated containers, and the text has been inevitably replaced by the image and the action. In this context, the thesis questions that the new sense of criticism is to be the operator that accompanies the architectural design process. From the project, on the project, for the project, in the project, to the project, with the project. An operator which undertakes the critical work from the architectural complexity, on the diversity, plurality, in the collective, to the simultaneous synthesis. To do this, the thesis is based on the notion of poetic -as complexity and internal synthesis- and in five architectural systems whose interaction cannot be ignored -field, program, material, geometry and morphology- to renovate and upgrade the usability of a critical method –the Mirregan-Todorov method- which has obtained recognized results, but whose heavy structure limits greatly its scope and operational. In this sense, it is not a purely analytical thesis. It neither tries to identify any architectural paradigms for this century. This research reformulates the role of criticism of architecture today. It runs from the open orderliness –as self-organization- of the poetic criticism to propose a line of work on the interaction of architectural systems in a synergistic manner and available to the project process. Since this attitude enables the production of a series of open mapping which reflect multiple current factors and agents of influence, this arrangement leads, as a final proposition, to raise the poetic criticism as a teaching and educational instrument of the subject of architectural design, where those maps lead to a complex, but approachable, vision of the project as a whole.

Twist grain boundaries in three-dimensional lamellar Turing structures

Steady spatial self-organization of three-dimensional chemical reaction-diffusion systems is discussed with the emphasis put on the possible defects that may alter the Turing patterns. It is shown that one of the stable defects of a three-dimensional lamellar Turing structure is a twist grain boundary embedding a Scherk minimal surface.