Fiber and matrix-dominant properties of fiber-reinforced polymer composites are important in many advanced technological fields, such as aviation, aerospace, transportation, energy industry, etc. Still, pre-mixing the polymer matrix with nanoparticles may enhance the through-thickness or matrix-dominant properties, and surface treatment of fiber reinforcements with nanoparticles, on the other hand, may improve the in-plane or fiber-dominated properties of laminated composites, as well as interfacial adhesion. A novel manufacturing method that combines a spraying process with nanoparticle/epoxy mixture technique was introduced to incorporate carbon nanoparticles for enhancement of thermal properties of multiscale laminates. Several graphene-based nanomaterials including graphene oxide (GO), reduced graphene oxide (rGO), graphene nanoplatelets (GNPs) and multi-walled carbon nanotubes (MWCNTs) were employed to modify the epoxy matrix and the surface of glass fibers. Multiscale glass fiber-reinforced composites were fabricated from unmodified and modified epoxy, as well as fibers, using the vacuum-assisted resin transfer molding (VARTM) process. The composites obtained combined improvements in both the fiber and matrix- dominant properties, resulting in superior composites. The morphological, rheological, thermal and mechanical properties of the glass fiber-reinforced multiscale composites were investigated. The thermal properties of the epoxy/nanoparticle composites were studied through differential scanning calorimetry (DSC), thermo-gravimetric analysis (TGA) and thermal conductivity measurements. The tensile, bending, vibration, interlaminar shear strength (ILSS) and thermal characterization results indicated that the introduction of GNPs, GO, rGO, and MWCNTs enhanced the themo-mechanical properties. The fracture surfaces of the fiber-reinforced composites were examined by scanning electron microscopy (SEM) and the micrographs were analyzed to comment on the mechanical results.

In this thesis, cadmium selenide (CdSe) quantum dots (QDs) are synthesized and characterized for patterning applications as well as for photovoltaic devices. The QDs were patterned and embedded into various polymers to form fluorescent composites. Their photophysical properties were investigated in detail. Through template assisted deposition the QDs-polymer composites were patterned into fluorescent nanorods. CdSe QDs were combined with multi-wall carbon nanotubes (CNTs) using a synthesized organic perylene derivative dye (N,N'-di(ethanethiol)-perylene-3,4,9,10-tetracarboxyl diimide) (ETPTCDI) as a link between QDs and CNTs. Upon testing, the QDs-ETPTCDI-CNTs nanocomposite displayed photoactive properties. Photophysical quenching studies of QD-ETPTCDI-CNTs provided better understanding of the electron-hole transfer of each component in the nanocomposite. The nanocomposite material was patterned onto microelectrode devices for photocurrent measurements under an AM1.5 solar simulated light source. These nanocomposites can be used as photovoltaic devices. The preliminary characterization studies of the device show excellent photoresponse under AM1.5 solar simulated light. The band gap alignment of each component of the nanocomposite and the charge transfer kinetics are the key to efficient electron-hole transfer. Optimization of the semiconducting material's interface can potentially make these nanocomposites a system for photovoltaic-based devices.

Cette thèse présente une étude théorique du transport de chaleur dans les matériaux composites nano poreux et nano fils ainsi qu'une étude théorique des propriétés thermoélectriques de l'alliage Si0:8Ge0:2 confrontée à des mesures expérimentales réalisées pour une partie, dans le cadre de l'étude.La première étude démontre que les alliages poreux affichent des réductions de conductivité thermique à des dimensions de pores beaucoup plus grandes que les matériaux poreux non alliés de même porosité nominale. Si on considère une taille de pores de 1000nm, la conductivité thermique de l'alliage Si0:5Ge0:5 avec 0:1 de porosité est deux fois plus faible que la conductivité thermique d'un matériau non poreux, alors que les pores plus petits que 100 nm sont nécessaires pour obtenir la même réduction relative dans le Si ou Ge pur. Nos résultats indiquent que les alliages nano poreux devraient être avantageux devant les matériaux nano poreux non alliés, et ceux pour les applications nécessitant une faible conductivité thermique, tels que les nouveaux matériaux thermoélectriques.La deuxième étude théorique sur la conductance thermique de nano fils révèle l'effet de la structure sur le transport des phonons. Avec un modèle théorique qui considère la dépendance en fréquence du transport des phonons, nous sommes en mesure quantitativement de rendre compte des résultats expérimentaux sur des nano fils droits et coudés dans la gamme de température qui montre qu'un double coude sur un fil réduit sa conductance thermique de 40% à la température de 5K. Enfin, nous avons procédé à une approche théorique des propriétés thermoélectriques des alliages SiGe frittés, en les comparant aux mesures expérimentales nouvelles et antérieures, tout en évaluant leur potentiel d'amélioration. L'approche théorique a été validée par comparaison de la mobilité prévue et la conductivité thermique prévues, en faisant varier la quantité de Ge et les concentrations de dopage, dans une gamme de température comprise entre 300 et 1000K. Nos calculs suggèrent qu'une optimisation par rapport à l'état de l'art actuel est possible pour le matériau de type n et type p, conduisant potentiellement à une augmentation de 6% (5%) du ZT _a 1000K et 25% (4%) _a température ambiante. Même des améliorations plus grandes devraient être possibles si la probabilité de diffusion des phonons aux joints de grains pouvait être augmentée au-delà de sa valeur actuelle de 10%. / This dissertation presents a theoretical study of heat transport in nanoporous composites andin nanowire and also theoretical study of thermoelectric properties of the Si0:8Ge0:2 alloywith some experimental new and old measurements.The first study on the porous alloys show that its can display thermal conductivity reductionsat considerably larger pore sizes than nonalloyed porous materials of the same nominalporosity. The thermal conductivity of Si0:5Ge0:5 alloy with 0.1 porosity becomes half thenonporous value at 1000 nm pore sizes, whereas pores smaller than 100 nm are required toachieve the same relative reduction in pure Si or Ge. Using Monte Carlo simulations, we alsoshow that previous models had overestimated the thermal conductivity in the small pore limit.Our results imply that nanoporous alloys should be advantageous with respect to nanoporousnonalloys, for applications requiring a low thermal conductivity, such as novel thermoelectrics.The second theoretical study on the nanowire thermal conductance reveals the structureeffect on the phonon transport. With a theoretical model that considers the frequency dependenceof phonon transport, we are able to quantitatively account for the experimental resultsof straight and bent nanowires in the whole temperature range which shows that due to andouble bend on the straight thermal conductance reduced by 40% at temperature 5K.Finally, we theoretically investigate the thermoelectric properties of sintered SiGe alloys,compare them with new and previous experimental measurements, and determine their potentialfor further improvement. The theoretical approach is validated by extensive comparisonof predicted bulk mobility, thermopower, and thermal conductivity, for varying Ge and dopingconcentrations, in the 300 �� 1000K temperature range. The effect of grain boundariesis then included for Si0:8Ge0:2 sintered nanopowders , and used to predict optimized valuesof the thermoelectric figure of merit at different grain sizes. Our calculations suggest thatfurther optimization of current state of the art n-type (p-type) material would be possible,possibly leading to 6% (5%) ZT enhancement at 1000K and 25% (4%) at room temperature.Even larger enhancements should be possible if the phonon scattering probability of the grainboundaries could be increased beyond its present value of 10%.

This work seeks to develop a bionanocompÃsito drawn from galactomannan and crystals nanocelulose, both obtained from Prosopis juliflora. Initially, carob pods were subjected to grinding, milling, heating, filtration and centrifugation in order to yield a viscous solution which, with the addition of ethanol, the precipitate was possible galactomannan. So all fractions, and galactomannan fiber capsules were separated. The gum obtained was lyophilized and characterized, as its composition, as well as the fibrous fractions. Further, the fibers of the capsules underwent the hydrothermal process mesquite, followed by a bleaching with H2O2 and NaOH solutions) and acidic hydrolysis (H2SO4 60% v / v) for extracting nanocelulose. After hydrolysis one estÃvl suspension nanocelulose characterized by TGA, XRD, FTIR and zeta potential was obtained. Then galactomannan films were prepared, starting from a 5% (w / v) polysaccharide solution using glycerol as plasticizer. Movies, nanocelulose were added at concentrations of 3, 5 and 7%, and evaluated the influence of the addition of the nanocrystals in the mechanical, thermal and barrier properties to water vapor. The galactomannan extracted from mesquite presented, respectively, in protein, lipid, ash and moisture content of 5.3%, 2.3%, 4.0% and 5.2% and characteristic thermal behavior, showing exothermic event to 284.7  C, typical of his degradation. Their functional groups identified by FTIR, and determination of its mass and molar ratio mannose / galactose. The fiber showed considerable differences in their levels of cellulose, hemicellulose, lignin, insoluble lignin, extractives, ash and moisture, after treatments. These results were corroborated by analysis of FTIR, XRD and TGA. And through the characterizations of the films, it was proved that there were improvements in the thermal, mechanical and barrier properties, the obtained biocomposites, with the addition of nanocelulose. / Este trabalho busca o desenvolvimento de um bionanocompÃsito elaborado a partir de galactomanana e cristais de nanocelulose, ambos obtidos da algaroba (Prosopis juliflora). Inicialmente, vagens da algaroba foram submetidas à trituraÃÃo, moagem, aquecimento, filtraÃÃo e centrifugaÃÃo obtendo-se uma soluÃÃo viscosa onde, com a adiÃÃo de etanol, foi possÃvel precipitar a galactomanana. EntÃo as fraÃÃes de interesse, galactomanana e fibra das cÃpsulas, foram separadas. A goma obtida foi liofilizada e caracterizada, quanto a sua composiÃÃo, assim como as fraÃÃes fibrosas. Na sequÃncia, as fibras das cÃpsulas da algaroba sofreram processo hidrotÃrmico, seguido de dois branqueamentos com soluÃÃes de NaOH e H2O2, e hidrÃlise Ãcida (H2SO4 60% v/v) para extraÃÃo de nanocelulose. ApÃs a hidrÃlise, foi obtida uma suspensÃo estÃvel de nanocelulose, caracterizada por TGA, DRX, potencial zeta e FTIR. EntÃo foram preparados filmes de galactomanana, a partir de uma soluÃÃo 5% (m/v) do polissacarÃdeo, utilizando glicerol como plastificante. Aos filmes, foram adicionados nanocelulose, nas concentraÃÃes de 3, 5 e 7%, e avaliado a influÃncia da adiÃÃo dos nanocristais nas propriedades mecÃnicas, tÃrmicas e de barreira a vapor de Ãgua. A galactomanana extraÃda da algaroba apresentou, respectivamente, teores de proteÃna, lipÃdio, cinzas e umidade de 5,3%, 2,3%, 4,0% e 5,2% e comportamento tÃrmico caracterÃstico, apresentando evento exotÃrmico a 284,7ÂC, tÃpico de sua degradaÃÃo. Seus grupos funcionais identificados por FTIR, alÃm da determinaÃÃo de sua massa molar e razÃo manose/galactose. A fibra apresentou considerÃveis diferenÃas nos seus teores de celulose, hemicelulose, lignina solÃvel, lignina insolÃvel, extrativos, cinzas e umidade, apÃs os tratamentos. Esses resultados foram corroborados por anÃlises de FTIR, DRX e TGA. AtravÃs das caracterizaÃÃes dos filmes, ficou comprovado que a adiÃÃo de nanocelulose melhorou propriedades tÃrmicas, mecÃnicas e de barreira, dos biocompÃsitos obtidos.

Compósitos são materiais híbridos que resultam de associações de, pelo menos, dois tipos deferentes de materiais. O desenvolvimento da sociedade humana somente atingiu o estágio atual utilizando-se de compósitos de todo o tipo de misturas de materiais. Além disso, o desenvolvimento de compósitos com partículas cada vez menores de fase reforçante com o passar das décadas, ou precisamente, dos séculos foram as principais razões do alcance do \"estado da arte\" da ciência dos compósitos. Com relação à ciência dos compósitos, os nanocompósitos são a grande descoberta do último meio século. Seguindo tendências dos estudos na área dos compósitos, este trabalho foca obter nanocompósitos de elastômero SBR (matriz elastomérica) com argilas tratadas e não tratadas. Além disso, a avaliação de propriedades mecânicas, térmicas, reológicas, de cura, em solução e propriedades de difração de raios-X são outro alvo deste trabalho. Os compósitos foram preparados com equipamentos tradicionais de processamento de elastômeros e, depois disso, suas propriedades foram avaliadas. Considerando propriedades em difração de raios-X, somente o compósito com Cloisite 20A mostrou estrutura intercalada. Os compósitos com argilas tratadas mostraram um melhor perfil geral de propriedades, com destaque novamente para o compósito com Cloisite 20A. Todos os compósitos com argilas tratadas mostraram um menor tempo de cura. Esse comportamento se deve à presença dos sais de tratamento orgânicos dos argilominerais que modificam a densidade de ligações cruzadas e a velocidade de cura. As melhores propriedades do compósito contendo Cloisite 20A, considerando que este foi o único a demonstrar estrutura intercalada, nos permitem concluir que um nanocompósito foi obtido nesta situação. / Composites are hybrid materials which result from associations of, at least, two different kind of materials. The human society development only achieved the current stage using composites of all type of materials mixing. Besides this, the achievement of composites with smaller particles of reinforcing phases along the decades or, precisely, along centuries were the main reasons to reach the current \"state of art\" of composites science. Regarded to composites science, the nanocomposites are the major breakthrough of the last half century. Following the trends of composites science study, this work is focused on obtain nanocomposites of SBR elastomer (rubber matrix) with treated and untreated clays. In addition to this, the evaluation of mechanical, thermal, reological, rubber cure, solution stability and X-Ray diffraction properties are other main target of this work. The composites were prepared with traditional equipments of rubber processing an after the properties were measured. Considering the X-Ray diffraction properties of obtained composites, only the composite with the organoclay Cloisite 20A showed an intercalated structure. The composites containing treated clays demonstrated the better mechanical, thermal and solution stability properties, with a special highlight to the composite containing Cloisite 20A. All composites obtained with organoclays showed lower cure time. This behavior is a result of organic treatment salts of organoclays presence that is able to modify crosslink density and the cure velocity. The better properties of composite containing Cloisite 20A, considering that this composite was the only one that showed intercalated structure, enable us to conclude that a nanocomposite was obtained in this situation.

Doctor of Philosophy / Department of Grain Science & Industry: Food Science Institute / Sajid Alavi / One of the worst pollution menaces of modern times is plastic packaging, because of its poor degradability. Packaging materials based on starch utilize the benefits of natural polymerization, abundant availability of raw material, and fast biodegradability. However, the highly hydrophilic nature and poor mechanical properties of starch based films limit their application. This problem was sought to be overcome by forming a nanocomposite of starch and layered silicate clay. This study utilizes melt extrusion processing to synthesize starch-clay nanocomposites for biodegradable packaging films and investigate the effects of chemical compatibility of starch, plasticizer and nanoclay and melt extrusion conditions on the structure and properties of composite films. In the first part of the study, the influence of clay type, clay content, starch source and amylose content was investigated. Starch-montmorillonite (MMT) hybrids showed an intercalated nanostructure due to the compatibility of the two components and led to cast film with higher tensile strength and better water vapor barrier properties as compared to starch-organically modified montmorillonite (I30E) hybrids, as well as native starch only. With increase in clay content (0-21 wt%), significantly higher (15-92%) tensile strength (TS) and lower (22-67%) water vapor permeability (WVP) were obtained. The results indicated that nanocomposite technology could be applied to improve the properties of starch-based packaging films. The barrier and mechanical properties of nanocomposite films did not vary significantly with different starch sources (corn, wheat and potato starch), whereas films from regular corn starch showed better properties than either high amylopectin or high amylose-based nanocomposite films. The second part of the study investigated the effects of glycerol content (0-20 wt%) and three plasticizers (glycerol, urea, formamide) on the structure and properties of the starch-clay nanocomposite films. With decreasing glycerol content, the extent of clay exfoliation increased. Films with 5% glycerol exhibited the lowest WVP, and the highest TS and glass transition temperature (Tg). The use of urea and formamide improved the dispersion of clay platelets. Compared to glycerol and urea, formamide has an intermediate hydrogen bond forming ability with starch. However, at the same level of plasticizer (15 wt%), formamide plasticized nanocomposite films exhibited the lowest WVP, highest TS and Tg. Results indicated that a balance of interactions between starch, clay surface modifications and plasticizers might control the formation of nanocomposite structure, and in turn affect the performance of the nanocomposite films. The last part of the study investigated the effects of extrusion conditions (screw configuration, barrel temperature profile, screw speed and barrel moisture content) on the structure and properties of the starch-clay nanocomposite films. Increasing the shear intensity significantly improved the exfoliation and dispersion of clay platelets. The combination of lowest barrel moisture content (20%) and high shear screw configuration exhibited almost complete clay exfoliation and the lowest WVP and highest TS of all treatments. Increasing the barrel temperature also improved clay exfoliation and performance of films. The results suggested that, when polymer and clay are chemically compatible, optimization of process conditions (shear intensity, temperature etc.) can enable significant improvement in clay exfoliation and dispersion and the performance of nanocomposite films.

At the author’s request, the abstract has been removed due to the confidential nature of the thesis. It will be added once the embargo period has passed.

In this research work, the relationships between structure and properties in micro-composites and nano-composites of polyurethane (PU) and conductive carbon particles have been studied. PU is a class of block copolymers containing the urethane linkage (-NHCO-O-) within its structure. Most PU block copolymers consist of alternating ‘soft’ and ‘hard’ segments. The hard segment used in this study was based on 4,4’-methylenebisphenylisocyanate (MDI) and 2-methyl 1,3 propanediol (MP-Diol) which produced a stiff aromatic polyurethane. Two soft segments; poly(tetrahydofuran) (PTHF) and poly(propylene oxide) based polyol end-capped with ethylene oxide (PPO-EO) were used to study the effects of soft segment structure on PU properties. DMTA, DSC and modulated-DSC indicated that PU-PTHF had higher microphase separation due to greater immiscibility between PTHF and the MDI/MP-Diol hard segments. In order to improve the electrical and mechanical properties of PU, conductive carbon particles were incorporated. The critical factor was the dispersion of these conductive fillers in the PU matrix to obtain optimum properties. The first carbon filler studied was carbon black (CB). PU composites prepared by the adding of MP-Diol plus ultrasonication (MU) gave the best dispersion of CB aggregates resulting in higher thermal decomposition temperature and good conductivity. However, the mechanical toughness was reduced. In subsequent studies, PU composites incorporating three different treated multiwalled carbon nanotubes (MWCNT) were investigated. MWCNT were disentangled and shortened by ultrasonication and acid cutting treatments. The ultrasonicated MWCNT (MWCNT_U) had longer length than the acid-cut MWCNT (MWCNT_AC). Ultrasonication was the best technique for dispersing MWCNT since the storage modulus was increased by ~200% at low MWCNT_U loading and the toughness remained the same as unfilled PU. PU/MWCNT_AC nanocomposites at 1 – 3 wt% of MWCNT_AC exhibited similar electrical conductivities to unfilled PU at an order of 10-8 S/cm, implying that the acid cutting treatment might disturb the inherent conductivity in MWCNT. The conductive percolation thresholds of composites were determined following the percolation theory. It was found that the percolation thresholds for MWCNT-filled composites were significantly lower than that of CB-filled composites. The lowest percolation threshold was observed in MWCNT_U-filled composite at 0.31 wt%.

Membrane technology is one of the most promising technologies for addressing the global water crisis as well as in many other applications. One of the drawbacks of current ultra- and nanofiltration membranes is the relatively broad pore size distribution. Block copolymer membranes with ultrahigh permeability and very regular pore sizes have been recently demonstrated with pores being formed by the supramolecular assembly of core/shell micelles. Our study aimed at developing an innovative and economically efficient alternative method to fabricate isoporous membrane by self-assembly of magnetic nanoparticle with a polystyrene shell, mimicking the behavior of block copolymer micelle. Fe3O4 nanoparticles of ~13 nm diameter were prepared by co-precipitation as cores. The initiator for ATRP was covalently bonded onto the surface of magnetic nanoparticles with two strategies. Then the surface initiated ATRP of styrene was carried out to functionalize nanoparticles with polystyrene through a “grafting from” method. Finally, the nanocomposite membrane was cast from 50 wt % Fe3O4@PS brush polymer solution in DMF via non solvent phase inversion. Microscopies reveal an asymmetric membrane with a dense thin layer on top of a porous sponge-like layer. This novel class of asymmetric membrane, based on the pure assembly of functionalized nanoparticles was prepared for the first time. The nanoparticles are well distributed however with no preferential order yet in the as-cast film.I would like to thank my committee chair and advisor, Prof. Suzana Nunes, and other committee members, Prof. Klaus-Viktor Peinemann and Prof. Gary Amy, for their guidance and support throughout the course of this research. My appreciation also goes to my colleagues in our group for useful discussions and suggestions. I also want to extend my gratitude to the staff from the KAUST Core Lab for Advanced Nanofabrication, Imaging and Characterization, especially Dr. Ali Reza Behzad, Dr. Rachid Sougrat, and Dr. Long Chen, for their assistance for various microscopy measurements. Finally, my heartfelt gratitude is extended to my parents and all my friends. I cannot finish this thesis without their encouragement and support.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21795号 / 工博第4612号 / 新制||工||1718(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 辻井 敬亘, 教授 山子 茂, 教授 渡辺 宏 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM