Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

We propose new theoretical models, which generalize the classical Avrami-Nakamura models. These models are suitable to describe the kinetics of nucleation and growth in transient regime, and/or with overlapping of nucleation and growth. Simulations and predictions were performed for lithium disilicate based on data reported in the literature. One re-examined the limitations of the models currently used to interpret DTA or DSC results, and to extract the relevant kinetic parameters. Glasses and glass-ceramics with molar formulation 0.45SiO2? (0.45-x)MgO?xK2O?0.1(3CaO.P2O5) (0?x?0.090) were prepared, crystallized and studied as potential materials for biomedical applications. Substitution of K+ for Mg2+ were used to prevent devritification on cooling, to adjust the kinetics of crystallization and to modify the in vitro behaviour of resulting biomaterials. The crystallization of the glass frits was studied by DTA, XRD and SEM. Exothermic peaks were detected corresponding to bulk crystallization of whitlockite-type phosphate, Ca9MgK(PO4)7, at approximately 900ºC, and surface crystallization of a predominant forsterite phase (Mg2SiO4) at higher temperatures. XRD also revealed the presence of diopside (CaMgSi2O6 in some samples. The predominant microstructure of the phosphate phase is of the plate-type, seemingly crystallizing by a 2-dimensional growth mechanism. Impedance spectroscopy revealed significant changes in electrical behaviour, associated to crystallization of the phosphate phase. This showed that electrical measurements can be used to study the kinetics of crystallization for cases when DTA or DSC experiments reveal limitations, and to extract estimates of relevant parameters from the dependence of crystallization peak temperature, and its width at half height. In vitro studies of glasses and glass-ceramics in acelular SBF media showed bioactivity and the development of apatite layers The morphology, composition and adhesion of the apatite layer could be changed by substitution of Mg2+ by K+. Apatite layers were deposited on the surface of glass-ceramics of the nominal compositions with x=0 and 0.09, in contact with SBF at 37ºC. The adhesion of the apatite layer was quantified by the scratch test technique, having been related with SBF?s immersion time, with composition and structure of the glass phase, and with the morphology of the crystalline phase of the glass-ceramics. The structure of three glasses (x=0, 0.045 and 0.090) were investigated by MAS-NMR ( 29Si and 31P), showing that the fraction of Q3 structural units increases with the contents of Mg, and that the structure of these glasses includes orthophosphate groups (PO43-) preferentially connected to Ca2+ ions. Mg2+ ions show preference towards the silicate network. Substitution of Mg2+ by K+ allowed one to change the bioactivity. FTIR data revealed octacalcium phosphate precipitation (Ca8H2(PO4)6.5H2O) in the glass without K, while the morphology of the layer acquires the shape of partially superimposed hemispheres, spread over the surface. The glasses with K present a layer of acicular hidroxyapatite, whose crystallinity and needles thickness tend to increase along with K content. / São propostos novos modelos teóricos, que generalizam o modelo clássico de Avrami-Nakamura, apropriados para a cinética de nucleação e de crescimento em regime transiente, e/ou com sobreposição entre o estágio de nucleação e o de crescimento. Foram efectuadas simulações com base em resultados da literatura, reportados para o dissilicato de lítio. Foram examinadas as limitações dos métodos correntemente usados para obter estimativas de parâmetros cinéticos, com base em resultados de ATD. Desenvolveram-se e investigaram-se vidros e materiais vitrocerâmicos susceptíveis de aplicação biomédica com a formulação molar 0.45SiO2?(0.45-x)MgO?xK2O?0.1(3CaO.P2O5) (0?x?0.090), preparados mediante a substituição de Mg2+ por K+. A cristalização das fritas de vidro foi estudada por ATD, DRX e SEM. Foram detectados picos exotérmicos correspondentes à cristalização de fosfato (cristalização em volume) do tipo whitlockite Ca9MgK(PO4)7 a aproximadamente 900ºC, e de forsterite (Mg2SiO4) acompanhada de alguma diopside (CaMgSi2O6; cristalização superficial) a temperaturas superiores. A microestrutura predominante da fase fosfato é do tipo placa, aparentando cristalizar por um mecanismo de crescimento bidimensional. Foi usada espectroscopia de impedâncias para monitorizar a cristalização em condições em que os ensaios de ATD ou de DSC revelam limitações, recorrendo a alterações significativas de propriedades eléctricas associadas à cristalização da fase de fosfato. Os vidros e vidros cerâmicos desenvolvidos revelaram bioactividade em meio acelular in vitro, desenvolvendo camadas apatíticas em SBF. A morfologia, composição e aderência da camada de apatite pôde ser modulada com base na substituição parcial de Mg2+ por K+. Foram depositadas camadas de apatite sobre vidros ceramizados (x=0 e 0.09), em SBF a 37ºC. A adesão da camada de apatite foi quantificada pela técnica de indentação deslizante tendo sido relacionada com o tempo de imersão em SBF, com a composição e estrutura da fase vítrea, e com a morfologia da fase cristalina dos vidros cerâmicos. Foi investigada a estrutura de três vidros (x=0, 0.045 e 0.090) por MAS-RMN (29Si e 31P), verificando-se que nos vidros mais ricos em Mg, a participação da unidade estrutural Q3 é mais significativa, e que a estrutura dos vidros inclui grupos ortofosfato (PO43-) mais próximos de iões Ca2+ do que dos iões Mg2+, sendo estes incorporados preferencialmente na rede de silicato. A substituição parcial de Mg2+ por K+ permitiu ajustar a cristalização dos materiais vitrocerâmicos e modular a bioactividade pretendida. Resultados de FTIR revelaram precipitação de fosfato octacálcico (Ca8H2(PO4)6.5H2O) no vidro sem K, enquanto que a morfologia da camada adquire a forma de hemisférios parcialmente sobrepostos, espalhados sobre a superfície. Os vidros com K apresentam uma camada de hidroxiapatite acicular, cuja cristalinidade e espessura de agulhas tende a aumentar com o teor de K.

The diploma thesis deals with the concept of a high-frequency chamber which serves for desiccation of emulsion consisted of oil and water where the contents of water is over 30% of the emulsion capacity. The high-frequency chamber works on frequency 2,45 GHz. The task was to design a numerical model in which a high-frequency thermic conjugated problem is solved. The design of a high-frequency chamber is made up considering the heat distribution in inhomogeneous environment as well as chemical and physical changes. The proportions of the high-frequency chamber can guarantee the biggest output transmitted from the source to the chamber with the emulsion desiccated and uniform layout of electromagnetic field. These criteria are necessary for smooth heating of the emulsion desiccated. In this diploma thesis, there were several numerical models with various proportions made up. Finally, the one with the shortest time of heating the emulsion in reference to emulsion capacity was chosen.

Aujourd’hui, les applications de stockage de données utilisent principalement deux types de matériaux : les chalcogénures pour le stockage optique (e.g. Blu-Ray) et le silicium pour le stockage électronique (e.g. mémoires Flash). Malgré le fait qu’ils se soient avérés les plus efficaces pour des applications répandues, ces matériaux ont des limitations. Récemment, avec la montée en puissance du graphene, les allotropes du carbone ont été étudiés à la fois pour leurs propriétés intrinsèques et pour des applications ; ils ont des propriétés électroniques, thermiques et mécaniques très intéressantes qui peuvent rendre ces matériaux plus efficaces que les chalcogénures ou le silicium pour certaines applications. Dans cette thèse, nous étudions la faisabilité et le potentiel du carbone comme matériau pour le stockage de données.Nous nous concentrons d’abord sur le développement de stockage optique. Nous découvrons que les lasers continus et pulsés peuvent être utilisés pour induire des changements de phase réversibles dans des couches minces de carbone, confirmant la possibilité d’utiliser le carbone comme un matériau pour le stockage optique. De plus, nous découvrons plusieurs nouveaux phénomènes, que nous expliquons en utilisant des techniques de caractérisation avancées et de la modélisation par ordinateur de la propagation thermique dans le carbone.Ensuite, nous nous concentrons sur le stockage de données électronique en développant des mémoires à base de graphene qui peuvent être dans deux états de résistance bien séparés pour un grand nombre de cycles. Pour évaluer le potentiel de cette technologie, on caractérise le mécanisme de changement de résistance et on développe un modèle électromécanique qui permet de prédire les meilleures performances atteignables : ces mémoires ont le potentiel de commuter bien plus rapidement que les mémoires Flash tout en étant non-volatiles. / Today, data storage applications rely mainly on two types of materials: chalcogenides for optical storage (e.g. Blu-Ray) and silicon for electronic storage (e.g. Flash memory). While these materials have proven to be the most efficient for widespread applications, both have limitations. Recently, with the rise of graphene, carbon allotropes have been studied both for their intrinsic properties and for applications; graphene and other carbon allotropes have very interesting electronic, thermal and mechanical properties that can make these materials more efficient than either chalcogenides or silicon for certain applications. In this thesis, we study the feasibility and potential of the usage of carbon as a data storage material.Firstly, we focus on developing optical data storage. It is found that both continuous-wave and pulsed lasers can be used to induce reversible phase changes in carbon thin films, thus opening the way toward carbon-based data storage. Along the way, several phenomena are discovered, shown and explained by using advanced characterization techniques and thermal modelling.Secondly, we focus on electronic data storage by developing graphene-based memories that are found to switch reliably between two well-separated resistance states for a large number of cycles. To assess the potential of this new technology, we characterize the switching mechanism and develop an electro-mechanical model enabling to predict the best performances attainable: these memories would potentially be much faster than Flash memories while playing the same role (non-volatile storage).

The trend in the electronic and electrical equipment industry towards denser and more powerful product requires a higher level of performance from cooling devices. In this context, passive cooling techniques such as latent heat storage systems have attracted considerable attention in recent years. Phase change materials (PCMs) have turned out to be extremely advantageous in this regard as they absorb high amount of latent heat without much rise of temperature. But unfortunately, nearly all phase change materials (PCMs) with high latent heat storage capacity have unacceptably low thermal conductivity, which makes heating and cooling processes slow during melting and solidification of PCMs. Augmentation of heat transfer in a PCM is achieved by inserting a high thermal conductivity material, known as thermal conductivity enhancer (TCE), into the PCM. The conglomeration of PCM and TCE is known as a thermal storage unit (TSU). In this thesis, detailed and systematic analyses are presented on the thermal performance of TSUs subjected to two types of thermal loading- (a) constant power loading in which a constant power level is supplied to the chip (heater) for a limited duration of time, and (b) cyclic loading. Eicosane is used as the PCM, while aluminium pin or plate fins are used as TCEs. First, a 1-D analytical model is developed to obtain a closed-form temperature distribution for a simple PCM domain (without TCE) heated uniformly from the bottom. The entire heating process is divided into three stages, viz. (a) sensible heating period before melting, during which heat is stored in the solid PCM in the form of specific heat, (b) melting period, during which a melt front progresses from the bottom to the top layer of the PCM and heat is stored in latent as well as in sensible forms, and (c) post melting period, during which energy is stored again in the form of sensible heat. For each stage, conduction energy equation is solved with a set of initial and boundary conditions. Subsequently, a resistance capacitance model of phase change process is developed for further analysis. For transient performance under constant thermal loading, experimental investigations are carried out for TSUs with different percentages of TCE. A numerical model is developed to interpret the experimental results. The thermal performance of a TSU is found to depend on a number of geometrical parameters and boundary conditions. Hence, a systematic approach is desirable for finding the best TSU design for which the chip can be operated for a longer period of time before it reaches a critical temperature (defined as the temperature above which the chip starts malfunctioning). As a first step of the approach, it is required to identify the parameters which can affect the transient process. It is found that the convective heat transfer coefficient, ‘h’ and the exposed area for heat transfer have little effect on the chip temperature during the constant power operation. A randomized search technique, Genetic Algorithm (GA), is coupled with the CFD code to find an optimum combination of geometrical parameters of TSUs based on the design criteria. First, the optimization is carried out without considering melt convection within the PCM. It is found that the optimum half-fin width remains fixed for a given heat flux and temperature difference. Assuming a quasi steady process, the results of optimization are then explained by constructing and analyzing a resistance network model. The resistance network model is then extended to include the effect of melt convection, and it is shown that the optimum pitch changes with the strength of convection. Accordingly, numerical analysis is carried out by considering the effect of melt convection, and a correlation for optimum pitch is developed. Having established the role of melt convection on the thermal performance of TSUs, rigorous computational and experimental studies are performed in order to develop correlations among different non-dimensional numbers, such as Nusselt number, Rayleigh number, Stefan number and Fourier number, based on a characteristic length scale for convection. The enclosures are classified into three types, depending on the aspect ratio of cavity, viz. shallow, rectangular and tall enclosures. For a shallow enclosure, the characteristic length is the height of cavity whereas for a tall enclosure, the characteristic length is the fin pitch. In case of rectangular enclosure, both pitch and height are the important characteristic lengths. For cyclic operation, it is required that the fraction of the PCM melting during the heating cycle should completely solidify back during the cooling period, in order that that TSU can be operated for an unlimited number of cycles. If solidification is not complete during the cooling period, the TSU temperature will tend to rise with every cycle, thus making it un-operational after some cycles. It is found that the solidification process during the cooling period depends strongly on the heat transfer coefficient and the cooling surface area. However, heat transfer coefficient does not play any significant role during the heating period; hence a TSU optimized for transient operation may not be ideal for cyclic loading. Accordingly, studies are carried out to find the parameters which could influence the behaviour of PCM under cyclic loading. A number of parameters are identified in the process, viz. cycle period and heat transfer coefficient. It is found that the required heat transfer coefficient for infinite cyclic operation is very high and unrealistic with air cooling from the surface of the TSU. Otherwise, the required cooling period for complete re-solidification will be very high, which may not be suitable for most applications. In an effort to bring down the cooling period to a duration that is comparable to the heating period, a new design is proposed where both ‘h’ and area exposed to heat transfer can be controlled. In this new design, the gaps between the fins in a plate-fin TSU are alternately filled with PCM, such that only one side of a fin is in contact with PCM and the other side is exposed to the coolant (air). In this arrangement, the same heat flow path through the fin which is used for heating the PCM (during the heating stage) can also be used for cooling and solidifying the PCM during the cooling part of the cycle. Natural or forced air cooling through the passages can be introduced to provide a wide range of heat transfer coefficient which can satisfy the cooling requirements. With this arrangement, the enhanced area provided for cooling keeps the ‘h’ requirement within a realistic limit. This cooling method developed is categorized as a combination of active and passive cooling techniques. Analytical and numerical investigations are carried out to evaluate the thermal performance of this modified PCM-based heat sink in comparison to the ones with conventional designs. It is found that, the performance of new PCM-based heat sink is superior to that of the conventional one. Experiments are performed on both the conventional and the new PCM-based heat sinks to validate the new findings.