The Voter and Chen version of an embedded-atom model, derived by fitting to experimental data of both the diatomic molecule and bulk platinum simultaneously, has been applied to study the locally stable structures, energetics, growth patterns and melting behavior of free platinum clusters in the size range of N=2-56 and N=75. Using the constant-energy molecular dynamics simulations, thermal and conjugate-gradient minimization techniques, the global minima and the other locally stable structures have been distinguished from those stationary structures that correspond to saddle points of the potential energy surface. The number of isomers and the probabilities of sampling different basins of attractions of the clusters from 2 to 22 atoms are obtained. The energy spectra of these clusters have been analyzed. The correlations between the total energy of the 75-atom cluster and the isomer number and the energy-spectrum-width of the isomers are investigated. The number of isomers of 75-atom cluster as a function of the total energy is presented, and the isomer probability distribution is discussed. The melting behavior of Pt_N clusters in the size range of N=12-14, 54-56, and N=75 has been studied. An atom-resolved analysis method including physical quantities such as the root-mean-square bond-length fluctuations and the coordination numbers for indivudual atoms as the functions of the temperature has been presented. Comparisons have been made with the results of previous calculations using electronic structure and empirical potential methods. The results show that the global minima have structures based on either octahedral, decahedral or icosahedral packing.

Les mémoires à base de semi-conducteur sont indispensables pour les dispositifs électroniques actuels. La demande croissante pour des dispositifs mémoires fortement miniaturisées a entraîné le développement de mémoires non volatiles fiables qui sont utilisées dans des systèmes informatiques pour le stockage de données et qui sont capables d'atteindre des débits de données élevés, avec des niveaux de dissipation d'énergie équivalents voire moindres que ceux des technologies mémoires actuelles.Parmi les technologies de mémoires non-volatiles émergentes, les mémoires à changement de phase (PCM) sont le candidat le plus prometteur pour remplacer la technologie de mémoire Flash conventionnelle. Les PCM offrent une grande variété de fonctions, comme une lecture et une écriture rapide, un excellent potentiel de miniaturisation, une compatibilité CMOS et des performances élevées de rétention de données à haute température et d'endurance, et peuvent donc ouvrir la voie à des applications non seulement pour les dispositifs mémoires, mais également pour les systèmes informatiques à hautes performances. Cependant, certains problèmes de fiabilité doivent encore être résolus pour que les PCM se positionnent comme un remplacement concurrentiel de la mémoire Flash.Ce travail se concentre sur l'étude de mémoires à changement de phase intégrées afin d'optimiser leurs performances et de proposer des solutions pour surmonter les principaux points critiques de la technologie, ciblant des applications à hautes températures. Afin d'améliorer la fiabilité de la technologie, la stœchiométrie du matériau à changement de phase a été conçue de façon appropriée et des dopants ont été ajoutés, optimisant ainsi la stabilité thermique. Une diminution de la vitesse de programmation est également rapportée, ainsi qu'un drift résiduel de la résistance de l'état de faiblement résistif vers des valeurs de résistance plus élevées au cours du temps.Une nouvelle technique de programmation est introduite, permettant d'améliorer la vitesse de programmation des dispositifs et, dans le même temps, de réduire avec succès le phénomène de drift en résistance. Par ailleurs, un algorithme de programmation des PCM multi-bits est présenté. Un générateur d'impulsions fournissant des impulsions avec la tension souhaitée en sortie a été conçu et testé expérimentalement, répondant aux demandes de programmation d'une grande variété de matériaux innovants et en permettant la programmation précise et l’optimisation des performances des PCM. / Semiconductor memory has always been an indispensable component of modern electronic systems. The increasing demand for highly scaled memory devices has led to the development of reliable non-volatile memories that are used in computing systems for permanent data storage and are capable of achieving high data rates, with the same or lower power dissipation levels as those of current advanced memory solutions.Among the emerging non-volatile memory technologies, Phase Change Memory (PCM) is the most promising candidate to replace conventional Flash memory technology. PCM offers a wide variety of features, such as fast read and write access, excellent scalability potential, baseline CMOS compatibility and exceptional high-temperature data retention and endurance performances, and can therefore pave the way for applications not only in memory devices, but also in energy demanding, high-performance computer systems. However, some reliability issues still need to be addressed in order for PCM to establish itself as a competitive Flash memory replacement.This work focuses on the study of embedded Phase Change Memory in order to optimize device performance and propose solutions to overcome the key bottlenecks of the technology, targeting high-temperature applications. In order to enhance the reliability of the technology, the stoichiometry of the phase change material was appropriately engineered and dopants were added, resulting in an optimized thermal stability of the device. A decrease in the programming speed of the memory technology was also reported, along with a residual resistivity drift of the low resistance state towards higher resistance values over time.A novel programming technique was introduced, thanks to which the programming speed of the devices was improved and, at the same time, the resistance drift phenomenon could be successfully addressed. Moreover, an algorithm for programming PCM devices to multiple bits per cell using a single-pulse procedure was also presented. A pulse generator dedicated to provide the desired voltage pulses at its output was designed and experimentally tested, fitting the programming demands of a wide variety of materials under study and enabling accurate programming targeting the performance optimization of the technology.

Le cerveau humain est composé d’un grand nombre de réseaux neuraux interconnectés, dont les neurones et les synapses en sont les briques constitutives. Caractérisé par une faible consommation de puissance, de quelques Watts seulement, le cerveau humain est capable d’accomplir des tâches qui sont inaccessibles aux systèmes de calcul actuels, basés sur une architecture de type Von Neumann. La conception de systèmes neuromorphiques vise à réaliser une nouvelle génération de systèmes de calcul qui ne soit pas de type Von Neumann. L’utilisation de mémoire non-volatile innovantes en tant que synapses artificielles, pour application aux systèmes neuromorphiques, est donc étudiée dans cette thèse. Deux types de technologies de mémoires sont examinés : les mémoires à changement de phase (Phase-Change Memory, PCM) et les mémoires résistives à base d’oxyde (Oxide-based resistive Random Access Memory, OxRAM). L’utilisation des dispositifs PCM en tant que synapses de type binaire et probabiliste est étudiée pour l’extraction de motifs visuels complexes, en évaluant l’impact des conditions de programmation sur la consommation de puissance au niveau du système. Une nouvelle stratégie de programmation, qui permet de réduire l’impact du problème de la dérive de la résistance des dispositifs PCM est ensuite proposée. Il est démontré qu’en utilisant des dispositifs de tailles réduites, il est possible de diminuer la consommation énergétique du système. La variabilité des dispositifs OxRAM est ensuite évaluée expérimentalement par caractérisation électrique, en utilisant des méthodes statistiques, à la fois sur des dispositifs isolés et dans une matrice complète de mémoire. Un modèle qui permets de reproduire la variabilité depuis le niveau faiblement résistif jusqu’au niveau hautement résistif est ainsi développé. Une architecture de réseau de neurones de type convolutionnel est ensuite proposée sur la base de ces travaux éxperimentaux. La tolérance du circuit neuromorphique à la variabilité des OxRAM est enfin démontrée grâce à des tâches de reconnaissance de motifs visuels complexes, comme par exemple des caractères manuscrits ou des panneaux de signalisations routières. / The human brain is made of a large number of interconnected neural networks which are composed of neurons and synapses. With a low power consumption of only few Watts, the human brain is able to perform computational tasks that are out of reach for today’s computers, which are based on the Von Neumann architecture. Neuromorphic hardware design, taking inspiration from the human brain, aims to implement the next generation, non-Von Neumann computing systems. In this thesis, emerging non-volatile memory devices, specifically Phase-Change Memory (PCM) and Oxide-based resistive memory (OxRAM) devices, are studied as artificial synapses in neuromorphic systems. The use of PCM devices as binary probabilistic synapses is studied for complex visual pattern extraction applications, evaluating the impact of the PCM programming conditions on the system-level power consumption.A programming strategy is proposed to mitigate the impact of PCM resistance drift. It is shown that, using scaled devices, it is possible to reduce the synaptic power consumption. The OxRAM resistance variability is evaluated experimentally through electrical characterization, gathering statistics on both single memory cells and at array level. A model that allows to reproduce OxRAM variability from low to high resistance state is developed. An OxRAM-based convolutional neural network architecture is then proposed on the basis of this experimental work. By implementing the computation of convolution directly in memory, the Von Neumann bottleneck is avoided. Robustness to OxRAM variability is demonstrated with complex visual pattern recognition tasks such as handwritten characters and traffic signs recognition.

O design de produto através de suas interfaces multidisciplinares possibilita o desenvolvimento de novas tecnologias destinadas a pessoas com deficiência física. A Tecnologia Assistiva (TA) engloba todo arsenal de recursos e serviços que contribuem para proporcionar ou ampliar habilidades funcionais de pessoas com deficiência e tem como principal exemplo a cadeira de rodas, onde o usuário fica longos períodos na posição sentada e o conforto térmico é necessário. Neste trabalho, desenvolveu-se microcápsulas de eicosano e impregnou-se espumas de poliuretano (PU) com as microcápsulas visando o conforto térmico nessas espumas. O eicosano é um material de mudança de fase (PCM) com temperatura de mudança de fase ao redor de 37°C, que é igual a temperatura de equilíbrio térmico do corpo humano. As microcápsulas inseridas em espumas de poliuretano possuem potencial uso na Tecnologia Assistiva, mais especificamente em assentos de cadeiras de rodas visando o conforto térmico. As microcápsulas foram obtidas através da polimerização in-situ, utilizando resina melamina-formaldeído como invólucro e eicosano como núcleo. As técnicas usadas para a caracterização das microcápsulas envolveram análises de microscopia óptica, microscopia eletrônica de varredura (MEV), granulometria, Espectroscopia do Infravermelho por Transformada de Fourier (FT-IR), Análise Termogravimétrica (TGA) e Calorimetria Exploratória Diferencial (DSC). As microcápsulas de eicosano foram então inseridas em espumas de poliuretano com diferentes densidades e foram analisadas por termografia. As microcápsulas de eicosano impregnadas nas espumas de PU possuem capacidade de absorver ou liberar calor do ambiente circundante e manter a temperatura ao seu redor constante por um determinado período de tempo, sendo assim possuem aplicação potencial na Tecnologia Assistiva, como em assentos de cadeiras de roda por exemplo, devido a sua capacidade de isolamento térmico e absorção ou liberação de calor enquanto ocorre a mudança de fase do eicosano. / The product design through its multidisciplinary interfaces allows de development of new technologies for people with some physical disability. The Assistive Technology (TA) includes all the resources and services that contribute to give and enlarge the functional abilities of people with some disability. The most significant sample of TA resource is the wheel chair, where the person stays long time in the seat position and the thermal comfort is necessary. In this work, microcapsules of eicosane were developed and then polyurethane foams were impregnated with the microcapsules aiming the thermal comfort on the polyurethane foams. The eicosane is a phase change material (PCM) with temperature of phase change of 37°C which is similar to the human body temperature in thermal equilibrium. The microcapsules added to the polyurethane foams have potential use on the Assistive Technology, more specifically on cushion seats aiming the thermal comfort. The microcapsules were obtained by in-situ polymerization using resin melamine-formaldehyde as wall and eicosane as the core. The analysis used to evaluate the properties of the microcapsules were: optical microscopy, scanning electron microscopy (SEM), particle size analysis, fourier transform infrared spectroscopy (FT-IR), thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). Then the microcapsules of eicosane were added in polyurethane foams with different densities and were analyzed by infrared thermography. The microcapsules of eicosane added to the polyurethane foams present the capacity of absorb or release heat to the environment and maintain the around temperature constant for a period of time. So they have potential application on the Assistive Techology, as wheel chair cushion seats for example, due to its capacity of thermal insulation and absorption or release of heat while occurs the eicosane phase change.

Les Mémoires ont de plus en plus importance à l'époque actuelle, et sont fondamentales pour la définition de tous les systèmes électroniques avec lesquels nous entrons en contact dans notre vie quotidienne. Les mémoires non-volatiles (NVM), représentées par la technologie Flash, ont pu suivre jusqu'à présent l'effort à la miniaturisation pour satisfaire la demande croissante de densité de mémoire exigée par le marché. Cependant, la réduction de la taille du dispositif de mémoire est de plus en plus difficile et la complexité technologique demandé a augmenté le coût par octet. Dans ce contexte, les technologies de mémoire innovantes deviennent non seulement une alternative, mais la seule solution possible pour fournir une densité plus élevée à moindre coût, une meilleure fonctionnalité et une faible consommation d'énergie. Les Mémoires à Changement de Phase (PCM) sont considérées comme la solution de pointe pour la future génération de mémoires non-volatiles, grâce à leur non-volatilité , scalabilité, "bit-alterability", grande vitesse de lecture et d'écriture, et cyclabilité élevée. Néanmoins, certains problèmes de fiabilité restent à surmonter afin de rendre cette technologie un remplacement valable de la technologie Flash dans toutes les applications. Plus en détail, la conservation des données à haute température, est l'une des principales exigences des applications embarquées industrielles et automobiles. Cette thèse se concentre sur l'étude des mémoires à changement de phase pour des applications embarquées, dans le but d'optimiser le dispositif de mémoire et enfin de proposer des solutions pour surmonter les principaux obstacles de cette technologie, en abordant notamment les applications automobiles. Nous avons conçu, fabriqué et testé des dispositifs PCM basés sur des structures reconnues et innovantes, en analysant leurs avantages et inconvénients, et en évaluant l'impact de la réduction de la taille. Notre analyse de fiabilité a conduit au développement d'un système de caractérisation dédié à caractériser nos cellules PCM avec des impulsions de l'ordre de la nanoseconde, et à la mise en oeuvre d'un outil de simulation basé sur un solveur thermoélectrique et sur l'approche numérique "Level Set", pour comprendre les différentes mécanismes qui ont lieu dans nos cellules pendant les opérations de programmation. Afin de répondre aux spécifications du marché des mémoires non-volatiles embarquées, nous avons conçu le matériau à changement de phase intégré dans le dispositif PCM avec deux principales approches: la variation de la stoechiométrie et l'ajout de dopants. Nous avons démontré et expliqué comment la rétention des données dans les dispositifs PCM à base de GeTe peut être améliorée avec l'augmentation de la concentration de Te, et comment les inclusions de SiO2 peuvent réduire les défauts causés par la tension de lecture à températures de fonctionnement élevées. En outre, nous avons présenté les avantages sur la réduction de la puissance de programmation du dopage de carbone dans les dispositifs à base de GST. Enfin, nous avons étudié les effets de l'enrichissement en Ge dans le GST, combiné avec le dopage N et C, intégré dans des cellules PCM à l'état de l'art. Grâce à l'introduction d'une nouvelle technique de programmation, nous avons démontré la possibilité d'augmenter la vitesse de programmation de ces dispositifs, caractérisés par des performances de rétention des données parmi les meilleurs rapportés dans la littérature, et de réduire le phénomène de la dérive de la résistance qui affecte la stabilité de l'état programmé des cellules PCM. Nous avons donc prouvé, avec ces derniers résultats, la validité de la technologie PCM pour les applications embarquées. / Memories are getting an exponential importance in our present era, and are fundamental in the definition of all the electronic systems with which we interact in our daily life. Non-volatile memory technology (NVM), represented by Flash technology, have been able to follow till now the miniaturization trend to fulfill the increasing memory density demanded by the market. However, the scaling is becoming increasingly difficult, rising their cost per byte due to the incoming technological complexity. In this context, innovative memory technologies are becoming not just an alternative, but the only possible solution to provide higher density at lower cost, better functionality and low power consumption. Phase-Change Memory (PCM) technology is considered the leading solution for the next NVM generation, combining non-volatility, scalability, bit-alterability, high write speed and read bandwidth and high cycle life endurance. However, some reliability issues remain to overcome, in order to be a valid Flash replacement in all the possible applications. In particular, retention of data at high temperature, is one of the main requirements of industrial and automotive embedded applications. This work focuses on the study of embedded Phase-Change Memories, in order to optimize the memory device and finally propose some solutions to overcome the main bottlenecks of this technology, in particular addressing automotive applications. We designed, fabricated, and tested PCM devices based on recognized and innovative structures, analyzing their advantages and disadvantages, and evaluating the scaling impact. Our reliability analysis led to the development of a characterization setup dedicated to characterize our PCM cells with pulses in the order of nanoseconds, and to the implementation of a simulation tool based on a thermoelectrical solver and on the Level Set numerical approach, to understand the different mechanisms taking place in our cells during the programming operations. In order to fulfill embedded NVM requirements, we engineered the phase-change material integrated in the PCM device with two main approaches: the stoichiometry variation and the dopants addition. We showed and explained how the data retention in GeTe based PCM devices can be enhanced increasing Te content, and how SiO2 inclusions can reduce the read voltage disturbs at high operating temperatures. Moreover, we reported the advantages on the programming power reduction of carbon doping in GST based devices. Finally, we studied the effects of Ge enrichment in GST, combined with N or C doping, integrated in state of the art PCM cells. Through the introduction of a new programming technique, we demonstrated the possibility to improve the programming speed of these devices, characterized by data retention performance among the best reported in the literature, and to reduce the drift phenomenon that affects the resistance state stability of PCM technology. We then proved, with these last results, the suitability of PCM for embedded applications.

O design de produto através de suas interfaces multidisciplinares possibilita o desenvolvimento de novas tecnologias destinadas a pessoas com deficiência física. A Tecnologia Assistiva (TA) engloba todo arsenal de recursos e serviços que contribuem para proporcionar ou ampliar habilidades funcionais de pessoas com deficiência e tem como principal exemplo a cadeira de rodas, onde o usuário fica longos períodos na posição sentada e o conforto térmico é necessário. Neste trabalho, desenvolveu-se microcápsulas de eicosano e impregnou-se espumas de poliuretano (PU) com as microcápsulas visando o conforto térmico nessas espumas. O eicosano é um material de mudança de fase (PCM) com temperatura de mudança de fase ao redor de 37°C, que é igual a temperatura de equilíbrio térmico do corpo humano. As microcápsulas inseridas em espumas de poliuretano possuem potencial uso na Tecnologia Assistiva, mais especificamente em assentos de cadeiras de rodas visando o conforto térmico. As microcápsulas foram obtidas através da polimerização in-situ, utilizando resina melamina-formaldeído como invólucro e eicosano como núcleo. As técnicas usadas para a caracterização das microcápsulas envolveram análises de microscopia óptica, microscopia eletrônica de varredura (MEV), granulometria, Espectroscopia do Infravermelho por Transformada de Fourier (FT-IR), Análise Termogravimétrica (TGA) e Calorimetria Exploratória Diferencial (DSC). As microcápsulas de eicosano foram então inseridas em espumas de poliuretano com diferentes densidades e foram analisadas por termografia. As microcápsulas de eicosano impregnadas nas espumas de PU possuem capacidade de absorver ou liberar calor do ambiente circundante e manter a temperatura ao seu redor constante por um determinado período de tempo, sendo assim possuem aplicação potencial na Tecnologia Assistiva, como em assentos de cadeiras de roda por exemplo, devido a sua capacidade de isolamento térmico e absorção ou liberação de calor enquanto ocorre a mudança de fase do eicosano. / The product design through its multidisciplinary interfaces allows de development of new technologies for people with some physical disability. The Assistive Technology (TA) includes all the resources and services that contribute to give and enlarge the functional abilities of people with some disability. The most significant sample of TA resource is the wheel chair, where the person stays long time in the seat position and the thermal comfort is necessary. In this work, microcapsules of eicosane were developed and then polyurethane foams were impregnated with the microcapsules aiming the thermal comfort on the polyurethane foams. The eicosane is a phase change material (PCM) with temperature of phase change of 37°C which is similar to the human body temperature in thermal equilibrium. The microcapsules added to the polyurethane foams have potential use on the Assistive Technology, more specifically on cushion seats aiming the thermal comfort. The microcapsules were obtained by in-situ polymerization using resin melamine-formaldehyde as wall and eicosane as the core. The analysis used to evaluate the properties of the microcapsules were: optical microscopy, scanning electron microscopy (SEM), particle size analysis, fourier transform infrared spectroscopy (FT-IR), thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). Then the microcapsules of eicosane were added in polyurethane foams with different densities and were analyzed by infrared thermography. The microcapsules of eicosane added to the polyurethane foams present the capacity of absorb or release heat to the environment and maintain the around temperature constant for a period of time. So they have potential application on the Assistive Techology, as wheel chair cushion seats for example, due to its capacity of thermal insulation and absorption or release of heat while occurs the eicosane phase change.

Apresentamos neste trabalho uma série de estudos sobre os efeitos de perturbações geométricas em alguns modelos da física estatística com transições de fase contínuas, Essas perturbações são causadas por distribuições aleatórias ou aperiódicas (e determinísticas) de campos ou de acoplamentos microscópicos ao longo das redes em que os modelos são definidos. No caso de sistemas aperiódicos sem desordem, mostramos uma grande quantidade de exemplos das possíveis alterações induzidas no comportamento crítico de modelos de Ising, Potts e um modelo para polímeros em interação. Empregamos técnicas não-perturbativas de grupo de renormalização no espaço real (matrizes de transferência para estudar a termodinâmica desses sistemas na região crítica ou tricrítica. Concluímos que, ainda que distribuições aperiódicas de constantes de acoplamento muitas vezes alterem sensivelmente os expoentes críticos associados às transições de fases, classificações universais ainda são possíveis. As classes de universalidade ligadas aos diferentes modelos e às várias maneiras de perturbá-los aperiodicamente estão associadas n inesperadas estruturas atratoras que surgem no espaço hamiltoniano de parâmetros, descritas em detalhe. No caso de modelos em presença de perturbações aleatórias à simetria translacional, argumentamos que alguns tipos de classificações universais também devem ser possíveis, primeiramente por causa de urna certa analogia com os sistemas aperiódicos anteriores, e também porque eles parecem sempre estar associados a formas de dinâmica complexa (corno a que se observa em sistemas vítreos não-desordenados). Comentamos brevemente sobre esta última conexão, e apresentamos urna análise ele um modelo desordenado muito simples, que tem a termodinâmica inteiramente calculável, e pode esconder alguma assinatura dessa dinâmica complexa. Finalmente. discutimos os rudimentos da chamada técnica de Martin-Siggia-Rose (MSR), que pode ser empregada para estudos avançados de sistemas com evoluções do tipo Langevin, e que permitiu o início da compreensão, já há algumas décadas, da possível universalidade da dinâmica complexa de sistemas desordenados. / We present in this work a series of studies on the effects of geometrical perturbations on statistical-physics models with continuous phase transitions. These perturbations are generated by random or aperiodic (deterministic) distributions of fields or microscopic couplings, along the lattices on which the models are defined. In case of non-disordered aperiodic systems, we s: show a wealth of examples of the changes that may be brought about on the critical behavior of Ising, Potts and interacting-polymer models. We employ non-perturbative real-space renormalization group techniques, as well as transfer-matrix methods to study the thermodynamics of such systems in the neighborhood of critical and tricritical points. Our conclusion is that although critical exponents may change appreciably in the presence of aperiodic distributions of couplings, universal classifications are nevertheless still workable. The universality classes associated to different models and the distinct ways of implementing aperiodicity are connected to unexpected attractors in Hamiltonian parameter space, which are thoroughly described. In case of random perturbations that break translational symmetry we argue that some universal classifications should still be possible. First, because these systems are in a sense analogous to the former aperiodic ones, and also because they always seem to be associated with some form of complex dynamics (as the dynamics of vitreous, non-random materials). We make some brief comments on this connection, and present a study of a very simpIe disordered model, whose thermodynamics is completely solvable, and which may hide some signatures of complex dynamics. Finally, we discuss the first steps of the so-called Martin-Siggia-Rose (MSR) method, which may be employed in advanced studies of systems undergoing Langevin-type evolutions, and which was responsible, some decades ago, for a first glimpse into the possible universality of complex dynamical behavior of disordered systems.

O design de produto através de suas interfaces multidisciplinares possibilita o desenvolvimento de novas tecnologias destinadas a pessoas com deficiência física. A Tecnologia Assistiva (TA) engloba todo arsenal de recursos e serviços que contribuem para proporcionar ou ampliar habilidades funcionais de pessoas com deficiência e tem como principal exemplo a cadeira de rodas, onde o usuário fica longos períodos na posição sentada e o conforto térmico é necessário. Neste trabalho, desenvolveu-se microcápsulas de eicosano e impregnou-se espumas de poliuretano (PU) com as microcápsulas visando o conforto térmico nessas espumas. O eicosano é um material de mudança de fase (PCM) com temperatura de mudança de fase ao redor de 37°C, que é igual a temperatura de equilíbrio térmico do corpo humano. As microcápsulas inseridas em espumas de poliuretano possuem potencial uso na Tecnologia Assistiva, mais especificamente em assentos de cadeiras de rodas visando o conforto térmico. As microcápsulas foram obtidas através da polimerização in-situ, utilizando resina melamina-formaldeído como invólucro e eicosano como núcleo. As técnicas usadas para a caracterização das microcápsulas envolveram análises de microscopia óptica, microscopia eletrônica de varredura (MEV), granulometria, Espectroscopia do Infravermelho por Transformada de Fourier (FT-IR), Análise Termogravimétrica (TGA) e Calorimetria Exploratória Diferencial (DSC). As microcápsulas de eicosano foram então inseridas em espumas de poliuretano com diferentes densidades e foram analisadas por termografia. As microcápsulas de eicosano impregnadas nas espumas de PU possuem capacidade de absorver ou liberar calor do ambiente circundante e manter a temperatura ao seu redor constante por um determinado período de tempo, sendo assim possuem aplicação potencial na Tecnologia Assistiva, como em assentos de cadeiras de roda por exemplo, devido a sua capacidade de isolamento térmico e absorção ou liberação de calor enquanto ocorre a mudança de fase do eicosano. / The product design through its multidisciplinary interfaces allows de development of new technologies for people with some physical disability. The Assistive Technology (TA) includes all the resources and services that contribute to give and enlarge the functional abilities of people with some disability. The most significant sample of TA resource is the wheel chair, where the person stays long time in the seat position and the thermal comfort is necessary. In this work, microcapsules of eicosane were developed and then polyurethane foams were impregnated with the microcapsules aiming the thermal comfort on the polyurethane foams. The eicosane is a phase change material (PCM) with temperature of phase change of 37°C which is similar to the human body temperature in thermal equilibrium. The microcapsules added to the polyurethane foams have potential use on the Assistive Technology, more specifically on cushion seats aiming the thermal comfort. The microcapsules were obtained by in-situ polymerization using resin melamine-formaldehyde as wall and eicosane as the core. The analysis used to evaluate the properties of the microcapsules were: optical microscopy, scanning electron microscopy (SEM), particle size analysis, fourier transform infrared spectroscopy (FT-IR), thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). Then the microcapsules of eicosane were added in polyurethane foams with different densities and were analyzed by infrared thermography. The microcapsules of eicosane added to the polyurethane foams present the capacity of absorb or release heat to the environment and maintain the around temperature constant for a period of time. So they have potential application on the Assistive Techology, as wheel chair cushion seats for example, due to its capacity of thermal insulation and absorption or release of heat while occurs the eicosane phase change.

Orientador: Kamal Abdel Radi Ismail / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-09T04:28:28Z (GMT). No. of bitstreams: 1 GonzalezBejarano_MarioElias_M.pdf: 3100005 bytes, checksum: 12668e0ddb58dbc3a200122e0c40da4b (MD5) Previous issue date: 2006 / Resumo: No presente trabalho estuda-se o fenômeno de mudança de fase de um PCM em placas paralelas que compõe um banco de gelo. Parâmetros importantes como o espaçamento entre as placas, a temperatura da placa, a temperatura do fluido de trabalho e a vazão, são considerados numa faixa variável. Desenvolveu-se um modelo numérico para simular o processo de solidificação com o objetivo de determinar a posição da frente de solidificação e a distribuição de temperaturas na fase sólida, além de avaliar a influência dos parâmetros considerados. As equações governantes, considerando transferência de calor unidimensional, foram discretizadas utilizando o método de diferenças finitas e o esquema modificado de espaço de tempo variável (MVTS) para a resolução da malha computacional. Considera-se a temperatura inicial do PCM igual à da solidificação e com propriedades constantes. A modelagem da solidificação foi feita para os casos de temperatura da superfície da placa constante e variável. Para validar o modelo numérico, foi construída uma bancada experimental onde foram feitos diversos testes com os parâmetros mencionados anteriormente. Os resultados numéricos obtidos foram analisados e comparados. Estes mostraram concordância satisfatória com os resultados experimentais para a modelagem realizada com temperatura da placa variável. Os resultados deste trabalho podem ser utilizados para o projeto de armazenadores de calor latente em geometrias planas / Abstract: In the present work, the phase change phenomenon of a PCM in parallel plates that compose an ice bank is studied. Important parameters such as the gap between the plates, the plate temperature, the temperature and flow of the secondary fluid are considered. A numerical model was developed to simulate the solidification process with the aim of determine the position of the solidification front and the temperatures distribution at the solid phase, moreover, to evaluate the influence of the considered parameters. The governing equations, considering one-dimensional heat transfer, had been discretized using the finite differences method and the modified variable time steps scheme (MVTS) to resolve the computational mesh. The PCM was considered initially at solidification temperature and with constant thermal properties. The solidification model was made for the cases of constant plate temperature and variable temperature. To validate the numerical model, an experimental device was constructed where many tests were carried through with the mentioned parameters. The numerical results were analyzed and compared. These ones show satisfactory agreement with the experimental results for the modeling carried through with variable plate temperature. The results of this work can be used for the project of latent heat storage systems with plain geometries / Mestrado / Engenharia Termica e Fluidos / Mestre em Engenharia Mecânica

A preparação de vetores sintéticos para terapia gênica envolve a encapsulação de DNA em pequenos volumes em altas concentrações e nessas condições sabe-se que as moléculas de DNA podem ser organizar formando estruturas líquido-cristalinas. Essas moléculas, uma vez incorporadas a célula devem difundir e vários trabalhos experimentais têm mostrado que essa difusão é limitada pelo tamanho dos fragmentos de DNA. É nesse contexto que soluções de DNA in vitro constituem um sistema modelo para o estudo de processos dinâmicos de difusão na fase isotrópica e na fase anisotrópica. Neste trabalho investigamos a difusão de fragmentos de DNA de 150 pares de base dispersos em água com concentrações variando no intervalo de 80 a 350 mg/ml, que se situam no domínio da fase isotrópica e da fase colestérica, passando uma região intermedi ária de coexistência de fases. Nessas soluções foi acrescentado sal, em concentração suciente para blindar as interações eletrostáticas repulsivas, de maneira que os fragmentos de DNA podem ser tratados como cilindros rígidos e não interagentes. A técnica de FRAP (Fluorescence Recovery After Photobleach) foi empregada para determinação do coeciente de difusão dos fragmentos de DNA que foram marcados com uma prova uorescente, que se intercala entre os nucleotídios por meio de uma ligação covalente. As imagens de FRAP foram analisadas segundo dois métodos diferentes para ajuste do perl de intensidade de luz na mancha de bleach, que pode ser dado por uma função gaussiana, no caso de um processo de difusão isotrópico, ou uma por uma função de Bessel modicada no caso de um processo de difusão anisotrópico. Na fase isotrópica a função gaussiana é a que melhor descreve o perl de intensidade de luz da mancha de bleach e o valor obtido para o coeciente de difusão dos fragmentos de DNA está em torno de 20 m2=s, que é um valor compatível com os valores encontrados na literatura para soluções de DNA com fragmentos de mesma dimensão na fase isotrópica. Na fase colestérica, a análise das imagens de FRAP mostrou que o perl de intensidade de luz é mais bem ajustado por uma função de Bessel modi- cada, permitindo a determinação dos coecientes, D1 e D2, que correspondem aos coecientes de difusão paralelo e perpendicular à direção de orientação molecular local, respectivamente. Nessa mesofase, os valores obtidos para o coeciente de difusão estão entre 101m2=s e 102m2=s, com uma anisotropia, D1=D2 = 12. Esses resultados são compatíveis com os obtidos para soluções de vírus fd na fase nemática. Também foram feitas medidas para amostras com composição que se situam na região intermediária entre a fase isotrópica e a fase colestérica e que podem apresentar duas ou até três fases em coexistência. A análise das imagens permitiu a identicação de processos de difus ão anisotrópico e isotrópicos, em uma mesma amostra, comprovando a coexistência de fases que não são identicadas apenas pela observação da textura em microscopia de luz polarizada. / Preparation of synthetic vectors for gene therapy applications implies encapsulation of DNA in small cavities in high concentrations and in these conditions DNA molecules self-organize forming liquid crystalline structures. Once incorporated to the cell, DNA must diuse in cytoplasm and many experimental work have demonstrated that such diusion is limited by the fragments size. In this context, DNA solutions can be regarded as a promising model system for investigating isotropic and anisotropic diusion. In this work we have investigated diusion of DNA fragments, (150 base pairs), dissolved in water, for concentrations varying from 80 mg/ml to 350 mg/ml, ranging the domains of isotropic and cholesteric phases, with an intermediary region of phase coexistence. Salt was added to the solution, in concentration high enough to screen repulsive electrostatic interactions allowing us to regard DNA fragments as non interacting rigid rods. FRAP (Fluorescence Recovery After Photobleach) technique was used to determine diusion coecients of DNA fragments marked with a uorescent probe, which binds covalently to the nucleotides. Analysis of FRAP images are performed following two possible ttings to the intensity prole in bleach zone, which can be a Gaussian function, for isotropic diusion, either a Bessel modied function if the diusion process is anisotropic. In the isotropic phase the Gaussian function was found to be more appropriate to describe the intensity prole in the bleach spot zone, resulting in a diusion coecient around 20 m2=s, which is compatible with values reported in literature for DNA solutions of fragments of the same dimension in the isotropic phase. Image analysis in the cholesteric phase has shown that light intensity prole of the bleach spot is best tted with a Bessel modied function, allowing us to determine two diusion coecients, D1 and D2, corresponding to the diusion coecients parallel and perpendicular to the local molecular orientation, respectively. In such mesophase the obtained values for the diusion coecients are around 101m2=s and 102m2=s, with an anisotropy; D1=D2 = 12. Such results are compatible with results obtained in the nematic phase of virus fd solutions. Solutions with concentrations lying in the intermediary zone presenting two or even three phase in coexistence were also investigated. By applying the two tting proles to the bleach spot it was possible to identify zones in the sample corresponding to isotropic diusion process and other zones presenting anisotropic diffusion process. This conrms the coexistence of isotropic and anisotropic phases, which cannot be identied only by optical polarized microscopy.