Submitted by Marlene Santos (marlene.bc.ufg@gmail.com) on 2014-12-18T18:07:39Z No. of bitstreams: 2 Tese - Aline Mendonça Pascoal - 2014.doc: 4428288 bytes, checksum: 759c80688c07f85efa0d5d3663f7dbec (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2014-12-22T10:33:16Z (GMT) No. of bitstreams: 2 Tese - Aline Mendonça Pascoal - 2014.doc: 4428288 bytes, checksum: 759c80688c07f85efa0d5d3663f7dbec (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2014-12-22T10:33:16Z (GMT). No. of bitstreams: 2 Tese - Aline Mendonça Pascoal - 2014.doc: 4428288 bytes, checksum: 759c80688c07f85efa0d5d3663f7dbec (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2014-03-28 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / This study was conducted to evaluate the chemical, physical-chemical, biochemical and rheological properties of starch from Solanum lycocarpum. The pulp from Solanum lycocarpum fruits was used as raw material for extraction of starch, resulting in a yield of 51%. The starch granules were heterogeneous in size, presenting a conical appearance, very similar to those from high-amylose cassava starch. The elemental analysis (CHNS) revealed 64.33% carbon, 7.16% hydrogen and 0.80% nitrogen. FT-IR spectroscopy showed the peaks characteristic of polysaccharides and NMR analysis confirmed the presence of the α-anomer of D-glucose. The S. lycocarpum starch was characterized by high value of intrinsic viscosity (3515 mPa s) and estimated molecular weight around 645.69 kDa. Furthermore, this starch was classified as a C-type and high amylose content starch, presenting 34.66% of amylose and 38% crystallinity. Endothermic transition temperatures (To = 61.25°C; Tp = 64.5°C; Tc = 67.5°C), gelatinization temperature (∆T = 6.3°C) and enthalpy changes (∆H= 13.21 J g−1) were accessed by DCS analysis. The thermogravimetric analysis of S. lycocarpum starch showed a typical three-step weight loss pattern. Microscopy revealed significant changes in the granule morphology after thermal treatment. Samples treated at 50°C for 10 min lost 52% of their crystallinity, which was partially recovered after storage for 7 days at 4°C. However, samples treated at 65°C for 10 min became were totally amorphous. This treatment was sufficient to completely disrupt the starch granule, as evidenced by the absence of an endothermic peak in the DSC thermogram. The RVA of S. lycocarpum starch revealed 4440.7 cP peak viscosity, 2660.5 cP breakdown viscosity, 2414.1 cP final viscosity, 834.3 cP setback viscosity, and a pasting temperature of 49.6°C. The low content of resistant starch (10.25%) and high content of digestible starch (89.78%) in S. lycocarpum suggest that this starch may be a good source for the production of hydrolysates, such as glucose syrup and its derivatives. These results make the S. lycocarpum fruit a very promising source of starch for biotechnological applications. / Este trabalho foi realizado para avaliar as propriedades químicas, físico- químicas, bioquímicas e reológicas do amido de Solanum lycocarpum. Polpas dos frutos de Solanum lycocarpum foram utilizadas como matéria-prima para a extração de amido, resultando em um rendimento de 51%. Os grânulos de amido apresentaram tamanho heterogêneo, com aparência cônica, muito semelhante ao amido de mandioca, com alto teor de amilose. A análise elementar (CHNS) revelou 64,33% de carbono, 7,16% de hidrogênio e 0,80% de nitrogênio. A espectroscopia FT-IR revelou picos característicos de polissacarídeos e a análise de RMN confirmou a presença do carbono αanomérico da D-glicose. O amido de S. lycocarpum apresentou elevada viscosidade intrínseca (3515 mPa s) e peso molecular estimado de 645,69 kDa. Além disso, este amido foi classificado como um amido do tipo C, apresentando 34,66% de amilose e 38% de cristalinidade. Através de análises por DCS determinou-se as temperaturas de transição endotérmica (To = 61,25°C; Tp = 64,5°C; Tc = 67,5°C), a variação da temperatura de gelatinização (∆T = 6,3°C) e a variação de entalpia (∆H = 13,21 J g-1). A análise termogravimétrica do amido de S. lycocarpum apresentou um padrão típico de perda de peso de três etapas. A microscopia revelou alterações significativas na morfologia dos grânulos após o tratamento térmico. As amostras tratadas a 50°C, durante 10 minutos, perderam 52% de sua cristalinidade, a qual foi parcialmente recuperada após armazenamento a 4°C, por 7 dias. No entanto, as amostras tratadas a 65°C, por 10 minutos, perderam totalmente sua cristalinidade, apresentando estrutura totalmente amorfa. Este tratamento foi suficiente para romper completamente o grânulo de amido, conforme evidenciado pela ausência do pico endotérmico na curva do DSC desta amostra. O RVA do amido de S. lycocarpum revelou um pico de viscosidade de 4440,7 cP, quebra de viscosidade 2660,5 cP, viscosidade final 2414,1 cP, tendência a retrogradação 834,3 cP e temperatura de pasta de 49,6°C. O baixo teor de amido resistente (10,25%) e o elevado teor de amido digerível (89,78%) sugerem que este amido pode ser uma boa fonte para a produção de hidrolisados, tais como xarope de glicose e seus derivados. Os resultados obtidos neste estudo fazem do fruto de S. lycocarpum uma fonte promissora de amido para aplicações biotecnológicas.

Submitted by Gabriela Lopes (gmachadolopesufpel@gmail.com) on 2016-10-10T18:10:31Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Tese Vania Zanela Pinto.pdf: 3876720 bytes, checksum: a2458e7baefb3806f5f42a1803a8a8b1 (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2016-10-11T20:56:35Z (GMT) No. of bitstreams: 2 Tese Vania Zanela Pinto.pdf: 3876720 bytes, checksum: a2458e7baefb3806f5f42a1803a8a8b1 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-10-11T20:56:35Z (GMT). No. of bitstreams: 2 Tese Vania Zanela Pinto.pdf: 3876720 bytes, checksum: a2458e7baefb3806f5f42a1803a8a8b1 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2014-08-04 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Os amidos mais comumente utilizados industrialmente, são o amido de milho, o de trigo, o de batata e o de mandioca. No entanto, amidos oriundos de fontes não convencionais têm despertado grande interesse de indústrias e cientistas. Isso, associado a possibilidade de expandir e modificar as propriedades do amido por tratamentos físicos, conferem aos amidos de pinhão e de feijão vantagens para o uso na indústria de alimentos. Outra possibilidade para a aplicação de amidos é a utilização destes como matéria-prima alternativa na produção de embalagens e compósitos poliméricos, bem como a produção de nanocristais (SNCs). O estudo foi composto damodificação (pré-tratamentos) e caracterização dos amidos de pinhão e feijão Carioca e subsequente hidrólise dos mesmos para a produção de nanocristais. Os pré-tratamentos com tratamento térmico de baixa umidade (TTBU), annealing (ANN)ultrassom (SNT) e hidrólise enzimática (ENZ) empregados objetivaram diminuir o tempo e/ou aumentar o rendimento de hidrólise, bem como alterar e/ou melhorar as propriedades dos nanocristais a serem produzidos. Os amidos apresentaram alterações nas propriedades de pasta, térmicas e mudança no padrão de difração de raio-X, variando conforme a modificação aplicada. Os nanocristais foram produzidos através de hidrólise ácida (H2SO4 3,0 M) por 5 e 7 dias à 40°C. O rendimento após a hidrólise variou entre 10,2-14,7 % para o amido de pinhão e 35,2-42,3 % para o amido de feijão o que aumentou a cristalinidade relativa. O TTBU e o SNT aumentam o rendimento dos SNCs mas promovem perdas na cristalinidade relativa dos mesmos, enquanto que, o ANN promove melhor estabilidade térmica dos SNCs. O amido de feijão se mostrou promissor para a produção de SNCs, principalmente pelo elevado rendimentoapós 5 dias de hidrólise com ácido sulfúrico. / The most common industrially used starches come from corn, wheat, potato, and cassava. Nevertheless, starches from non-conventional botanical origins are receiving more attention of industries and researchers. Associated with this interest, the possibility of expand and modify the starch properties through physical modifications provide for pinhão and Carioca beans advantages in food industry purposes. The use of theses starches as an alternative to raw materials derived from petroleum for packaging and polymer composites is another possible application. Also included in this possibility, there is the production of starch nanoparticles and nanocrystals (SNCs). This study consisted in modifications (pretreatment), characterization and subsequent hydrolysis of pinhão and Carioca bean starches to produce starch nanocrystals. The starch pretreatments of heat-moisture-treatment (HMT), annealing (ANN), sonication (SNT) and mild enzymatic hydrolysis (ENZ) were used to improve the starch nanocrystals characteristics, as well as decrease the acid hydrolysis time and/or increase the hydrolysis final yield. The pretreatments changed the paste, thermal, and crystallinity properties of the starches, which changed according to the modification applied (HTM, ANN, SNT and ENZ). The SNCs were made by 3 M H2SO4 at 5 and 7 days at 40°C and obtained from the resulted removal of the amorphous lamella from the starch granules, what increased the relative crystallinity. The achieved hydrolysis yields were between 10.2 to 14.7% for pinhão starch and 35.2 to 42.3% for Carioca bean. HMT and SNT pretreatments increased the SNCs yield, but they promote a decrease on the SNCs relative crystallinity, whereas the ANN promotes a better thermal stability, mainly due to the high yield after 5 days of sulfuric acid hydrolysis.

Les applications des nanoparticules métalliques nécessitent des assemblées monodisperses et stables sur un substrat tel que le graphène ou le graphite. Le graphène épitaxié sur métal (GEM) est étudié, car il facilite l'auto-organisation des adsorbats. La différence entre les mailles du graphène et du métal conduit à un effet de moiré contenant certaines régions favorables de l'adsorption. Ce travail est consacré surtout aux systèmes Ru-C et Pt-C où nous nous sommes intéressé au substrat du GEM nu, des agrégats y etant deposés et des agrégats métalliques sur graphite. Les potentiels d'ordre de liason permettent de mener des études en dynamique moléculaire sur des systèmes de taille réaliste à température finie. Dans le cas du système Pt-C une paramétrisation est disponible dans la littérature. Cependant, pour le système du Ru-C une paramétrisation sur la base de données DFT était nécessaire. Ce modèle atomistique néglige les forces de dispersion importantes pour des milieux étendus. Basé sur les modèles de Grimme, nous avons développé une description implicite tenant compte de la structure du substrat et son extension semi-infinie. De plus les effets d'écrantage importants pour des milieux métalliques sont pris en compte. Basé sur ce champ de force nous montrons des propriétés des adsorbats sur des substrats carbonés où nous évaluons le modèle de forces de dispersion. Grâce à des simulations de dynamique moléculaire, la stabilité des adsorbats et du graphène a été étudié dans le contexte de la dynamique vibrationnelle et de diffusion. En accord avec les expériences, la mobilité des adsorbats sur graphite s'avère élevée en comparaison avec des adsorbats sur GEM / Applications of metal nanoparticles require monodisperse and stable assemblies on a substrate such as graphene or graphite. Epitaxial graphene on metal (GOM) has attracted research interest because it contributes to the self-organisation of adsorbates. The difference in the lattice constants of graphene and metal leads to a moiré that contains certain regions that are favorable for adsorption. This work is mainly concerned with the Ru-C and Pt-C systems where we were interested in the bare substrate of GOM, adsorbates deposited thereon and metal clusters on graphite. Bond order potentials allow to carry out molecular dynamics studies for systems of realistic size and at finite temperature. In the case of the Pt-C, a parametrization is available in the literature. However, for Ru-C systems a custom parametrization effort based on data from electronic structure calculations was necessary. This atomistic model neglects long ranged dispersion forces that are important for adsorption phenomena on extended substrates. Based on the Grimme models, we developed an implicit description that takes the layered structure and the semi-infinite extension of the substrate into account. Also, screening effects that are important for metal materials are taken into account. Based on this force field, we show results concerning the properties of adsorbates on carbon substrates while evaluating the dispersion model. With the help of molecular dynamics simulations, the stability of adsorbates and graphene has been studied in the context of vibrational and diffusion dynamics. In agreement with experiments, the mobility of the adsorbates on graphite is high in comparison with adsorbates on GOM

Permafrost is a variable in Antarctic terrestrial ecosystems, and the role it plays in the cryosphere is not well understood. There is much still to be learnt about the thermal state, physical properties, thickness and age of permafrost in Western Dronning Maud Land (WDML). Active layer dynamics and observed change over time have the potential to improve our knowledge of climate change. Understanding the effects of a warming climate on permafrost can also be of benefit to infrastructure, especially in areas with a large amount of frozen ground such as Scandinavia, Canada and Russia. Active layer and permafrost dynamics of WDML, Antarctica, are presented and discussed using data from six study sites, namely the Robertskollen, Vesleskarvet, Flarjuven, Grunehogna, Slettjfell nunataks and the Troll research station in the Jutulsessen area. Ground and ambient air temperature, as well as ground moisture data were collected for each site. An inventory of active layer and permafrost landforms was compiled, as were the frequency of cycles over the zero-degree isotherm, and the depth of the active layer. Furthermore, 3D models, geo-referenced maps and Digital Elevation Models were created of study areas with the use of an Unmanned Aerial Vehicle (UAV). Polygonal features are the most common landscape feature and are common to most of the study sites. Robertskollen has the deepest active layer at over 66cm and Slettfjell the shallowest at 9cm. A maximum recorded air temperature of 8.76°C (10/11/2014) occurred at Troll with the second highest maximum of 6.77°C (22/12/2010) recorded at Vesleskarvet. Robertskollen has the highest observable biological growth and a maximum recorded ground temperature of 22.84°C (10/01/2014). Troll and Valterkulten, registered the second and third highest ground temperatures respectively. The high ground Temperature observed for Robertskollen may be ascribed to it being the lowest altitude site. The highest number of cycles over the zero-degree isotherm was observed at Troll (11.01%), followed by Robertskollen (10.99%). For relatively warm areas, such as Robertskollen it is recommended that two metre borehole loggers are installed in order to capture a detailed understanding of the active layer. The UAV proved to be a beneficial tool for capturing aerial photographs for post fieldwork analysis and 3D modelling.

Depuis longtemps, les dispositifs ou systèmes électromagnétiques sont omniprésents dans les milieux industriel et domestique. Le circuit magnétique de ces systèmes est un des éléments clefs d’une conversion énergétique efficace. Outre l’optimisation de la géométrie du circuit magnétique, la maîtrise de l’efficacité énergétique passe par l’utilisation de matériaux magnétiques performants et par une connaissance approfondie de leur comportement, notamment sous contraintes élevées comme les températures et fréquences élevées que l’on rencontre de plus en plus aujourd’hui. Notre travail s’intègre dans le cadre des recherches menées par l’équipe matériaux du laboratoire AMPERE, notamment sur les modèles comportementaux de matériaux magnétiques. Partant de nombreuses caractérisations expérimentales en fonction de la température, nous avons développé un modèle « dynamique » adapté à différents types de matériaux ferromagnétiques, et permettant de simuler rapidement l’influence de la température sur le fonctionnement permanent et transitoire de systèmes électromagnétiques simples. Il s’appuie sur l’association des modèles d’hystérésis de Jiles-Atherton et dit « tubes de flux ». Ce modèle, et la démarche associée de couplage entre phénomènes magnétique, thermique et électrique, sont validés sur un capteur de courant et une inductance. Les résultats confirment l’importance de l’effet de la température sur les performances des systèmes, et la pertinence de disposer d’un tel modèle pour optimiser ces systèmes / Since a long time, systems and electrical devices are everywhere in the industrial and domestic environments. The magnetic core of these systems is a key for achieving energy conversion efficiency. Apart from the geometry optimization, high performance materials are mandatory for obtaining an effective energy conversion, as well as deep knowledge of their behaviour. The choice of materials is even more important when strong constraints are imposed, like high temperature and high frequency, which are more and more met nowadays. Our work is taken on in the context of the research activity on the modeling of the behaviour of magnetic materials of the “materials” team of AMPERE-Lab. Starting from a large number of experimental characterizations of materials at different temperatures, we have developed a “dynamic” model adapted to the different kinds of magnetic materials, which allows to quickly simulate the effect of temperature on the steady-state and transient regime of simple electromagnetic systems. It is founded on using Jiles-Atherton’s hysteresis models together with the so called “flux tubes”. This modelling and the associated approach of coupling electrical, thermal and magnetic phenomena are validated on a current sensor and an inductance. The results confirm the importance of the effect of the temperature on the performances of systems, and the interest of having such a model so as to optimizing these systems

[pt] O objetivo deste trabalho foi avaliar as propriedades mecânicas, físicas e microestruturais de materiais compósitos cimentícios reforçados por fibras naturais e de laminados de bambu. O trabalho experimental foi direcionado para a determinação da tenacidade. Para se determinar a tenacidade foram utilizados três tipos de ensaios: impacto Charpy, impacto balístico e flexão em 3 pontos. Após os ensaios, a superfície de fratura dos corpos-de-prova foi analisada por microscopia eletrônica de varredura (MEV). Esta análise microestrutural serviu para determinar os modos de fratura e validar as hipóteses feitas nos modelos matemáticos utilizados. Foram usados modelos adaptados da literatura para a determinação da tenacidade e os valores teóricos obtidos foram confrontados com os experimentais. Determinou-se também através de modelos encontrados na literatura a tensão interfacial de todas as fibras utilizadas nesta pesquisa. Os modelos empregados para calcular a tenacidade e a tensão de adesão interfacial, se mostraram eficientes e válidos. Em segundo plano, porém não menos importante, ficou a determinação das propriedades térmicas dos materiais utilizados. Foram efetuados ensaios de condutividade térmica do compósito e ensaios termogravimétricos das fibras vegetais e do bambu. Os compósitos cimentícios foram reforçados por diferentes fibras naturais: polpa refinada de bambu (CPB), polpa de sisal (CPS), polpa de eucalipto (CPE), fibras curtas de sisal (CPFS) e wollastonita (CPW). As proporções das polpas de bambu, sisal e eucalipto utilizadas como reforço nas matrizes cimentícias foram de 8 por cento e 14 por cento em relação à massa do cimento, a da fibra curta de sisal (25 mm) foi de 3 por cento em relação ao volume e a da wollastonita foi de 11,5 por cento em relação à massa. Compóstios híbridos feitos com wollastonita e polpa de bambu (CPBW) foram também produzidos apenas variando a proporção da polpa de bambu em 8 por cento e 14 por cento e mantendo fixa a da wollastonita em 11,5 por cento. Como uma tentativa de se melhorar a resistência ao impacto, laminados CPB/AL foram também fabricados colando duas chapas de alumínio (liga 5052 H34) de espessura 0,8 mm em ambas às faces dos compósitos reforçados por fibra de bambu, formando assim compósitos sanduíche (CPBA). O bambu Moso (Phyllostachys heterocycla pubescens) com 5 anos de idade foi usado para fabricação dos laminados de bambu, sendo tratado com água fervida para a prevenção de ataques biológicos. Técnicas para a extração do laminado a partir de seu formato natural foram estudadas estabelecendo suas vantagens e desvantagens. Para o ensaio de impacto foram utilizados corpos-de-prova com dimensão nominal de 120 mm x 15 mm x 6 mm perfazendo um total de 18 corpos-de-prova. Para o de flexão foram realizados ensaios com uma lâmina simples de bambu (BL) e bambu laminado colado (BLC) com 3 camadas de lâminas dispostas ortogonalmente. Os resultados dos testes de impacto Charpy e flexão em 3 pontos comprovaram a boa tenacidade do bambu laminado quando submetido a cargas de impacto (42,54 kJ/m2) e a cargas estáticas (19,77 kJ/m2 para o laminado e 17,63 kJ/m2 para o laminado colado). Compósitos sanduíche constituídos de alumínio e laminados de bambu foram também fabricados. Estes foram analisados através de ensaios de impacto balísticos seguindo as recomendações da norma NIJ 0101.04. Observações no microscópico eletrônico de varredura foram realizadas para se analisar os mecanismos de falha dos laminados. / [en] The main objective of this work was to evaluate the mechanical, physical and microestructure properties of cementitious composite materials and bamboo laminates. The experimental program was focused on the determination of toughness. Three diferent types of tests were performed in order to establish it: Charpy impact, ballistic impact and three point bending test. After the tests, the fractured surface of the failed test specimens was observed using a Scanning Electron Microscope (SEM) to establish the failure mode. Mathematical models adapted from the available literature were used to determine the toughness from which the values were confronted to the ones obtained experimentally. It was also determined by mathematical models the interfacial bond stress of all fibers used in this research. The two models, used in the toughness and interfacial bond stress calculation, showed to be efficient, providing valid results. In second plan, but not less important, was the determination of the materials thermal properties. Thermal conductivity tests of the composites and thermogravimetry of the fibers and bamboo were performed. The cementitious composites were reinforced by different natural fibers: refined bamboo pulp (CPB), sisal pulp (CPS), eucalyptus pulp (CPE), short sisal fibers (CPFS) and wollastonite. The mass fraction of bamboo, sisal and eucalyptus pulp studied were 8 percent and 14 percent. For the wollastonite fiber the mass fraction studied was 11.5 percent and for the short sisal fiber a 3 percent volume fraction was studied. Hybrid composites made with wollastonite and bamboo pulp (CPBW) were also produced varying the bamboo fraction mass to 8 percent and 14 percent but keeping constant to 11.5 percent the wollastonite mass fraction. The slurry de-watering process was used in the production of all composites described before. To reduce the adverse effects of weathering on the cellulose fibers and to improve the impact load and flexural resistance of the composite, aluminum thin sheets were used to produce a sandwich composite lamina with the CPB, which was denominated as CPBA. Compound Adhesive gel from Otto Baumgart which is a type of epoxy was used to fix the aluminum sheets on the CPB. The use of aluminum has proved to give much higher impact resistance results when compared to the CPB ones. The 5 years old Moso bamboo (Phyllostachys heterocycla pubescens), which was previously treated in boiled water to eliminate biological agents, was used to produce the bamboo laminates. Techniques were developed to extract bamboo laminates from its natural form, establishing its advantages and disadvantages. For the Charpy impact test, a total of 18 specimens with nominal dimensions of 120 mm x 15 mm x 6 mm were tested. Laminated (BL) and 3 layer cross ply laminated bamboo (BLC) were tested in bending. A total of 9 specimens were tested per bamboo configuration. The BL specimens had nominal dimensions of 120 mm x 30 mm x 6 mm and the BLC were 120 mm x 30 mm x 17 mm. The results demonstrated the good toughness of bamboo laminates when subject to dynamic (42.54 kJ/m2) and to static load (19.77 kJ/m2 for the laminate and 17.63 kJ/m2 for the cross ply laminate). Aluminum thin sheets were again used to make sandwich composites, but now using the bamboo laminate (BLCA). The BLCA was tested using the ballistic impact test following the standard NIJ 0101.04. Analysis on the Scanning Eléctron Microscope (SEM) were performed in order to establish the laminate s failure mechanisms.

Cette thèse s'inscrit dans une démarche de maîtrise de l'énergie dans le secteur du bâtiment. Elle a pour but d'utiliser des solutions passives pour atteindre de hautes performances énergétiques. Une des solutions proposée, est l'utilisation de Matériaux à Changements de Phase (MCP) dans les parois. Les matériaux à formes stabilisée solide-liquide, sont utilisés pour stocker l'énergie thermique sous forme de chaleur latente. Le but de l'étude est de mettre en évidence l'impact réel des MCP en terme de complément d'isolation thermique et de proposer un modèle thermique pour prédire son impact sur le champ de température et par conséquent, sur le confort thermique. Une séquence expérimentale en environnement naturel et à grande échelle a été menée à l'île de La Réunion, où le climat est tropical et humide, avec un fort taux d'ensoleillement. Le rayonnement solaire étant important, il est nécessaire de minimiser les sollicitations solaires sur l'ensemble du bâtiment et en particulier la toiture, qui constitue la surface la plus exposée. La présence de lames d'airs au niveau de la toiture, qualifie celle-ci de complexe. Il est alors nécessaire de proposer une modélisation adaptée. Le modèle est couplé à un code de simulation thermique du bâtiment (ISOLAB) et permet de prédire d'une part, les profils de températures de chacune des surfaces constituant l'enveloppe du bâtiment, et d'autre part, d'évaluer l'impact des MCP sur le confort thermique pour différentes configurations. Selon une méthodologie, alliant Modélisation, Expérimentation et Validation (MEV), la démarche a permis de valider l'expérimentation dédiée et d'évaluer la capacité du modèle à prédire l'ensemble des données issues de l'expérimentation. / This Ph.D thesis focusses on energy control in buildings in order to reach high energetic performances by the use of passive means. One of the proposed solution is based on the use of Phase Change Materials (PCMs). Located into walls, PCMs allow to stock thermal energy into latent heat. The aim of the study is thus to put in evidence PCMs actual impacts on the thermal field of a building and its role as thermal insulation. For these considerations, a thermal model has been developed and validated. An experimental device has been set-up for the collection of data in field environment and for a human scale. The measurement sequence has been conducted at Reunion Island, for a hot and humid tropical climate. For the determination of the thermal behaviour of a commplex wall included PCMs, we proposed a generic model, able to predict many configurations. The model has been implemented in a multizone building simulation code (ISOLAB), for the prediction of wall temperature profiles and PCMs impact on the thermal comfort. Following a combined metholodogy, including modelling and experimentation for validation, we were able to validate the model for actual conditions and to evaluate the model's prediction accuracy.

Les origines de la variabilité des propriétés du matériau béton de chanvre sont nombreuses. On distingue celles liées aux propriétés des ses constituants et du matériau lui-même auxquelles il faut ajouter les dispersions qui résultent des méthodes utilisées pour caractériser ce béton. Ce travail de thèse, s’intéresse à l’étude de la variabilité des propriétés du béton de chanvre en tenant compte de ces différentes sources et en particulier au type de chènevotte utilisée. L’étude bibliographique réalisée permet de comprendre le matériau béton de chanvre, notamment ses constituants, les méthodes de caractérisations en usage ainsi que l’ampleur de la variabilité et de la sensibilité de ses propriétés vis-à-vis des différents paramètres. Cet état de l’art, permet en outre d’identifier les paramètres à considérer dans le cadre de cette thèse. Notre travail de thèse est alors subdivisé en 4 chapitres en plus de l’étude bibliographique. Dans le deuxième chapitre, une étude multicritère sur les propriétés des chènevottes est présentée. Après une campagne expérimentale de caractérisation de 13 types de chanvre, une analyse des résultats à deux niveaux est réalisée. Elle prend en compte, la masse volumique, la capacité d’absorption d’eau et la granulométrie. Dans un premier temps on présente les résultats de l’étude mono-caractéristique ; il s’agit de la comparaison d’une caractéristique donnée pour l’ensemble des chènevottes. Dans un second temps, on présente les résultats de l’étude multicritère. Il s’agit d’analyser l’ensemble des chènevottes en prenant en comptes les différentes caractéristiques à la fois. A l’issue, les chènevottes sont classées en trois groupes. Le chapitre 3 constitue une étude préliminaire tenant compte des différents paramètres sources de variabilités des propriétés du béton de chanvre, comme le laboratoire d’essai (équipements), la gâchée, la taille d’éprouvette et le type de chanvre. Les résultats obtenus montrent la nécessité d’étudier l’impact du type de la chènevotte. Par ailleurs, la dispersion considérable obtenue pour les résultats du module d’Young est vraisemblablement associée à sa méthode de calcul. Il devient alors important d’approfondir l’étude de son impact sur les valeurs du module d’Young obtenues. Le chapitre 4 vise justement à étudier les méthodes de calcul du module d’Young. Les différentes méthodes de la littérature sont alors utilisées pour exploiter les courbes contrainte-déformation dont les essais ont été réalisés dans les mêmes conditions. Les variabilités observées sur les résultats vis-à-vis de chacune des méthodes permettent alors de mettre en évidence leur impact et de proposer la méthode « flottante » comme étant la plus pertinente. Par ailleurs, un modèle permettant de décrire la loi de comportement mécanique du béton de chanvre est proposé. Il permet de déterminer la courbe enveloppe correspondant à la courbe expérimentale issue du chargement monotone, et permet également de reproduire la courbe expérimentale issue d’un chargement cyclique. Dans le dernier chapitre, en se basant sur les résultats du chapitre 2, neuf types de chanvre ont été sélectionnés pour la confection des éprouvettes de l’étude. Dans les mêmes conditions (fabrication et essai), il a été mis en évidence expérimentalement l’impact de la chènevotte sur les propriétés mécaniques avec un facteur égal à 10 entre les valeurs faibles et élevées. La réponse mécanique caractérisée par des faibles (<5%), moyennes (>5% et <8%) et fortes (>8% et <20%) niveau de déformation a été mis en évidence. Ces variabilités, restent cependant moins marquées pour la conductivité thermique et la masse volumique du béton de chanvre. L’étude met en évidence l’intérêt d’une étude approfondie sur l’interaction liant/chènevotte pour une meilleure compréhension de l’impact de la chènevotte sur le béton de chanvre. / The origins of the variability of hemp concrete material properties are numerous. They include among others those related to the properties of its constituents and material itself as well as the methods used for their characterizations. This thesis is interested in the study of the variability of hemp concrete properties taking into account these different parameters and in particular the type of hemp particles used. The litterature review corried out allowed to present the hemp concrete material, the properties of its constituents, their methods of characterization and also the extend of properties variability and sensitivity due to various parameters. Furthermore, it allowed to identify the parameters to be considered in the context of this thesis. Therefore, this thesis is devided into four chapters in addition to the literature review. In the second chapter, a multi-criteria study on the properties of hemp particles is presented. After an experimental study of characterization for 13 types of hemp particles, a two level analysis of result is performed. It takes into account the density, water absorption capacity and particle size distributions. First, the results of the single characteristic study are presented; it is about a comparison of a given characterstic for all hemp particles at the same time. Secondly, the results of the multi-criteria study are presented. In this last case, the analysis is corried out by taking into account all hemp particles and characteristics, both at the same time. The outcome of this study allowed to classify hemp particles into three groups from which, low, medium and high mechanical peformances are expected, respectively. Chapter 3 is a preliminary study taking into account various parameters as sources of variability for hemp concrete properties, such as the testing laboratory (equipments), the batch, the specimen size and hemp particles type. The obtained results highlight the need for further investigations about the impact of hemp particles type. Moreover, the considerable dispersion in the results of Young’s modulus is likely associated with its calculation method. It then becomes important to deepen the study of its impact on the values of Young’s modulus obtained. The chapter 4 aims to answer the problem found on the method for calculating the Young’s modulus. Various methods from literature are used to analyse the stress-strain curves from samples manufactured under the same conditions. The variability observed in results with respect to used method allowed to highlight their impact and to provide the floating method as the most pertinent since it presents less variability. In addition, a model to describe the mechanical behavior law of hemp concrete is proposed. It allows to determine the enveloppe curve which corresponds to experimental curve from the monotonic loading. It can also allow to reproduce the experimental curve from a cyclic loading. In the last chapter, based on the results of chapter 2, nine types of hemp particles were selected for the preparation and manufacturing of specimens of the study. Under the same conditions (manufacturing and test), it has been demonstrated experimentally the impact of hemp particles on mechanical properties with a factor 10 between low and high values from obtained results. The mechanical response characterized by low (<5%), medium (>5% and <8%) and high (> 8% and <20%) level of deformation have been highlighted. These variabilities remain, however less marked for thermal conductivity and density of hemp concrete material. This study highlights the interest of a comprehensive study on the interaction binder/hemp particles for a better understanding of the impact of hemp particles on hemp concrete.

Chalcogenide glass based Phase Change Memories (PCMs) are being considered recently as promising alternatives to conventional non-volatile Random Access Memories (NVRAMs). PCMs offer high performance & low power consumption, in addition to other advantages, such as high scalability, high endurance and compatibility with complementary metal oxide semiconductors (CMOS) technologies. Basically PCM is a resistance variable non-volatile memory in which the memory bit state is defined by the resistance of the material. In this case, the initial ‘OFF’ state (logic zero) corresponds to the high resistance amorphous state and the logic 1 or ‘ON’ state corresponds to low resistance crystalline state. The present thesis work deals with electrical, thermal, mechanical and optical characterization of certain tellurium based chalcogenide glasses in bulk and thin film form for phase change memory applications. A comparative study has been done on the electrical switching behavior of Ge-Te-Se & Ge-Te-Si amorphous thin film samples with their bulk counterparts. Further, electrical switching and thermal studies have been undertaken on bulk Ge-Te-Bi and Ge-Te-Sn series of samples. The composition dependence of switching voltages of bulk and thin film samples studied has been explained on the basis of different factors responsible for electrical switching. The thesis contains ten chapters: Chapter 1 deals with a brief introduction on chalcogenides and their applicability in phase change memories. The glass transition phenomenon, synthesis of chalcogenide alloys, different structural models of amorphous semiconductors and electrical switching behavior are also discussed in detail in this chapter. Further, a brief description of optical and mechanical properties along with the principles of few characterization techniques used is discussed. Also, a brief overview on PCM application of chalcogenides is presented. The second chapter provides the details of various experimental techniques used to measure electrical, thermal, optical and mechanical properties of few tellurium based chalcogenide glassy systems. In the third chapter, the electrical switching behavior of amorphous Al23Te77 thin film devices, deposited in co-planar geometry, has been discussed. It is found that these samples exhibit memory type electrical switching. Scanning Electron Microscopic studies show the formation of a crystalline filament in the electrode region which is responsible for switching of the device from high resistance OFF state to low resistance ON state. The switching behavior of thin film Al-Te samples is found to be similar to that of bulk samples, with the threshold fields of bulk samples being higher. This has been understood on the basis of higher thermal conductance in bulk, which reduces the Joule heating and temperature rise in the electrode region. Electrical switching and thermal behavior of bulk; melt quenched Ge18Te82-xBix glasses (1 ≤ x ≤ 4) are presented in chapter 4. Ge-Te-Bi glasses have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of these samples. A linear variation in switching voltages (also known as threshold voltages) (Vt) has been found with increase in thickness. The switching voltages have been found to decrease with an increase in temperature which is due to the decrease in the activation energy for crystallization at higher temperatures. Further, Vt of Ge18Te82-xBix glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of Vt, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe and Bi2Te3 phases. The fifth chapter deals with the electrical switching studies and optical band gap measurements on GexSe35-xTe65 (17 ≤ x ≤ 23) amorphous thin film samples. These thin film samples coated with sandwich geometry are found to switch with very low voltages as compared to bulk samples of the same chalcogenide glasses. The switching voltages and optical band gap are found to increase with the addition of Ge at the expense of Se. High structural cross linking with progressive addition of 4-fold coordinated Ge atoms could be the one of the reasons of increasing switching voltage and stronger Ge-Se bond strength could be the reason of increasing band gap for these chalcogenide glasses. In chapter 6, electrical switching studies on amorphous Ge15Te85-xSix (1 ≤ x ≤ 6) thin film samples have been described and the results are compared with their bulk counterparts. Similar trend has been found for both bulk and film samples when the threshold field is varied with composition. Optical band gap has been measured as a function of composition for these films, which also shows a behavior similar to that of switching voltages. The increasing trend in the variation with composition of electrical switching voltages and optical band gap are due to the increase in network connectivity and rigidity as Si atoms are incorporated into the Ge-Te system. Chapter 7 summarizes the electrical switching and glass forming ability of the Ge-Te-Sn glasses of two different composition tie-lines, namely Ge15Te85-xSnx and Ge17Te83-xSnx. Glasses belonging to both the series have been found to exhibit memory type of electrical switching behavior. The thickness dependence of threshold voltages is also found to support the memory switching behavior of the system. Further, ADSC studies are undertaken to explore the thermal behavior of these glasses which indicates that the crystallization tendency increases as Sn concentration is increased in the Ge-Te network. XRD studies done on two samples from both the series, reveal the fact that Sn atoms do not take part actively to enhance the network connectivity and rigidity. The composition dependence of crystallization temperature, metallicity factor and results of XRD studies are put together to explain the variation with composition of threshold voltages for both the series of samples. In chapter 8, investigations on the electrical switching behavior of Ge15Te85-xSnx (1 ≤ x ≤ 5) and Ge17Te83-xSnx (1 ≤ x ≤ 4) amorphous thin films have been discussed. Both the series of samples have been found to exhibit memory type of electrical switching behavior. The composition dependence of threshold voltage shows a decreasing trend, which has been explained on the basis of the Chemically Ordered Network (CON) model, bond strength and the metallicity factor. The optical band gap variation of both the series also exhibits a similar decreasing trend with composition. The observed behavior has been understood on the basis of higher atomic radius of Sn atom than Ge atom, which makes the energy difference between bonding and anti bonding state less at band edge. Chapter 9 deals with the nano-indentation studies on Ge15Te85-xSix (0 ≤ x ≤ 9) bulk glasses. The composition dependence of young’s modulus and hardness is studied systematically in this glassy system. The density of the samples of different compositions has also been measured, which strongly supports the variation of Young’s Modulus and hardness with composition. The composition dependence of mechanical properties of Ge-Te-Si samples has been understood on the basis of the presence of an intermediate phase and a thermally reversing window in this glassy system. A summary of the significant results obtained in the present thesis work is presented in the last chapter along with the scope for future work.

Gelfill (GF) is made of tailings, water, binder and chemical additives (Fillset, sodium silicate gel). The components of GF are combined and mixed on the surface and transported (by gravity and/or pumping) to the underground mine workings, where the GF can be used for both underground mine support and tailings storage. Thermal (T), hydraulic (H), and mechanical (M) properties are important performance criteria of GF. The understanding of these engineering properties and their evolution with time are still limited due to the fact that GF is a new cemented backfill material. In this thesis, the evolution of the thermal, hydraulic, mechanical, and microstructural properties of small GF samples are determined. Various binder contents of Portland cement type I (PCI) are used. The GF is cured for 3, 7, 28, 90, and 120 days. It is found that the thermal, hydraulic and mechanical properties are time-dependent or affected by the degree of binder hydration index. Furthermore, a relationship is found between the compressive strength and the saturated hydraulic conductivity of the GF samples. The unsaturated hydraulic properties of GF samples have also been investigated. The outcomes show that unsaturated hydraulic conductivity is influenced by the degree of binder hydration index and binder content, especially at low suction ranges. Simple functions are proposed to predict the evolution of air-entry values (AEVs), residual water content, and fitting parameters from the van Genuchten model with the degree of hydration index (α). Furthermore, two columns are built to simulate the coupled thermo-hydro-mechanical (THM) behaviour of GF under drained and undrained conditions. The obtained results from the GF columns are compared with the small samples. It is observed that the mechanical properties, hydraulic properties (suction and water content), and temperature development are strongly coupled. The magnitude of these THM coupling factors is affected by the size of the GF. The findings also show that the mechanical, hydraulic and thermal properties of the GF columns are different from samples cured in plastic moulds.