This research is directed toward determining the design space that is available for cellulose nanocrystals /poly(3-hydroxybutyrate)(CNC/PHB) composites. In order to develop this understanding, the processing-structure-properties relationships of CNC/PHB nanocomposites were examined at several different steps in a stepwise processing method. The as-processed morphology of solvent cast (SC) and anti-solvent compression molded (ASCM) samples were examined using DSC, optical microscopy and ATR-FTIR and the effect of processing and CNC addition on the isothermal and nonisothermal crystallization was examined using DSC, hot stage microscopy, and a novel fast scanning chip calorimeter, the Flash DSC. Results show that the addition of water during SC processing significantly reduced the rate of crystallization at both isothermal and nonisothermal conditions. This reduction in crystallization rate was due to the presence of water suppressed the intramolecular hydrogen bonding. Results from the experimenters performed also indicated CNCs act as a nucleating agent. Even though the overall kinetics of crystallization was increased with CNC addition, the growth rate of the spherulites was reduced with the addition of CNCs. Mechanical characterization of the ASCM and SC-EtOH samples showed that the differences in viscoelastic behavior with CNC addition for the ASCM samples but not the SC-EtOH samples. Also the strain to failure of both processing methods was increased with CNC addition. The knowledge that was obtained from this work can be used when designing processing protocols and heat treatments for PHB-based nanocomposites materials to allow greater control over crystallization processes and mechanical properties expanding opportunities for materials design.

Les films nanocomposites sont des revêtements composés de nanoparticules enrobées dans une matrice solide d’un matériau différent. L’intérêt de ces matériaux réside dans leur capacité à exploiter les caractéristiques inédites des nano-objets qu’ils contiennent tout en bénéficiant des propriétés de résistance mécanique et chimique de la matrice. Ces composites disposent de propriétés très prometteuses pour un grand nombre d’applications comme le photovoltaïque ou la photocatalyse. Plusieurs procédés de synthèse existants permettent de produire des matériaux nanocomposites par des méthodes physiques ou chimiques (co-pulvérisation, sol-gel,…). Cependant, aucun n’est assez flexible pour envisager la synthèse d’une large gamme de nanocomposites par le même procédé. Ceci est un frein au développement à l’échelle industrielle de ce type de matériaux. Le premier objectif de la thèse est de développer un procédé original de synthèse de films nanocomposites. Ce procédé présente un caractère universel en ce qu’il permet un choix a priori illimité dans la nature des nanoparticules et celle de la matrice. Le procédé développé combine un jet de nanoparticules sous vide formé par une lentille aérodynamique à un dispositif de pulvérisation magnétron qui permet de déposer la matrice. Le jet de nanoparticules permet de coupler toute source de nanoparticules à la pulvérisation. Les nanoparticules peuvent être soit synthétisées in situ en phase gazeuse, soit synthétisées préalablement en voie liquide. Une grande variété de nanoparticules peut donc être utilisée. La pulvérisation magnétron permet par ailleurs de disposer d’une très large gamme de matériaux pour la matrice (métaux, céramique, polymère). Dans le cadre de cette thèse, deux types de sources de nanoparticules ont été utilisés. Le premier est un réacteur de pyrolyse laser et le second un générateur d’aérosol. Le réacteur de pyrolyse laser permet une synthèse in-situ des nanoparticules en phase gazeuse alors que le générateur d’aérosol permet d’utiliser une suspension de nanoparticules préalablement synthétisées. Afin d’éprouver la robustesse du procédé de co-dépôt, deux types de matériaux nanocomposites ont été développés. Le premier matériau étudié est composé de nanoparticules d’or sphériques de 35 nm de diamètre, synthétisées préalablement par voix liquide, dans une matrice de silice. Le but ici est de bénéficier des propriétés optiques uniques des nanoparticules d’or dans un film résistant mécaniquement et chimiquement. Les caractérisations réalisées sur ces matériaux ont permis d’optimiser la concentration en nanoparticules d’or dans les films de manière à garder des propriétés mécaniques et chimiques compatibles avec les applications tout en gardant des propriétés optiques satisfaisantes. Le second type de matériaux étudiés est composé de nanoparticules semi-conductrices synthétisées in situ par pyrolyse laser et d’une matrice métallique. La synthèse de ce matériau permet de démontrer la flexibilité du procédé de co-dépôt à synthétiser une large gamme de films nanocomposites. Enfin, la robustesse du procédé ayant été démontrée, la conception d’un pilote industriel a été entreprise. Le but final étant de disposer d’une machine répondant aux exigences industrielles dans l’optique d’un transfert technologique. / The nanocomposite films are coatings of nanoparticles embedded in a solid matrix of a different material. The advantage of these materials is their ability to exploit the unique properties of nano-objects while benefiting of the mechanical and chemical resistance properties of the matrix. These composites have very promising properties for many applications such as photovoltaics and photocatalysis. Several existing synthetic methods can produce nanocomposite materials by physical or chemical methods (co-sputtering, sol-gel, ...). However, none is flexible enough to consider the synthesis of a wide range of nanocomposites by the same method. This is an obstacle to the development on an industrial scale of this type of material. The first objective of the thesis is to develop an original synthesis process of nanocomposite films. This method is universal in which it presents no limit in the choice of nanoparticles and matrix. The developed method combines vacuum nanoparticle jets formed by an aerodynamic lens with a magnetron sputtering device for depositing the matrix. The nanoparticle jets can be coupled with any source of nanoparticles. Nanoparticles may be synthesized in situ in the gas phase or beforehand solution synthesis. A wide variety of nanoparticles can be used. Magnetron sputtering also enables to have a very wide range of materials for the matrix (metal, ceramic, polymer). During this thesis, two types of nanoparticles sources were used. The first one is a laser pyrolysis reactor and the second is an aerosol generator. The laser pyrolysis reactor enables in-situ gas phase synthesis of the nanoparticles while the aerosol generator use a suspension of previously synthesized nanoparticles. To test the robustness of the co-deposition process, two types of nanocomposite materials have been developed. The first material is composed of 35 nm spherical gold nanoparticles, chemically synthesized, in a silica matrix. The goal here is to benefit from the unique optical properties of gold nanoparticles in a film mechanically and chemically resistant. The characterizations carried out on these materials have optimized the gold nanoparticle concentration in the films to keep the mechanical and chemical properties compatible with applications while maintaining satisfactory optical properties. The second type of materials studied is composed of semiconductor nanoparticles in situ synthesized by laser pyrolysis and a metal matrix. The synthesis of this material demonstrates the flexibility of the co-deposition method to synthesize a wide variety of nanocomposite films. Finally, the design of an industrial pilot was undertaken. The final goal is to have a pilot-scale setup that meets industry requirements in the context of a technology transfer.

Matériaux à base de graphène et d’oxyde de graphène ont attiré une grande attention depuis sa découverte. Cependant, comme la feuille de graphène a une surface spécifique élevée, il tend à former un agglomérat irréversible ou même empiler pour former le graphite par π-π empilage et Van-der Waals interactions. Les modifications doivent être faites pour séparer les feuilles de graphène sans apporter trop de dégâts dans sa structure aromatique. Dans cette thèse, nous avons lancé deux méthodes pour faire la modification du graphène, réaction de substitution nucléophile pour l’oxyde de graphène avec un C/O ~ 2 (FGS2), tandis que la demande électronique inverse réaction de Diels-Alder pour l’oxyde de graphène avec un très faible teneur en oxygène C/O ~ 20 (FGS20). Comme dans le second cas, FGS20 fonctionnalisés par tetrazine possède une excellente conductivité, il a été en outre combiné avec un polypyrrole pour fabriquer un matériau de supercondensateur.Dans le chapitre 2, nous avons greffé de manière covalente des dérivés de tétrazine à l'oxyde de graphène par substitution nucléophile. Comme l'unité de tétrazine est électroactif et riche en azote, avec un potentiel de réduction sensible du type de substituant et degré de substitution, nous avons utilisé l'électrochimie et la spectroscopie de photoélectrons X pour démontrer des preuves claires pour le greffage par liaison covalente. La modification chimique a été soutenue par spectroscopie infrarouge à transformée de Fourier et analyse thermique. Tétrazines greffé sur l'oxyde de graphène affichent différentes pertes de masse par rapport à graphène non modifiée et sont plus stables que les précurseurs moléculaires. Enfin, un dérivé de pontage tétrazine a été greffée entre des feuilles d'oxyde de graphène pour démontrer que la distance de séparation entre les feuilles peut être maintenue lors de la conception de nouveaux matériaux à base de graphène, y compris les structures d'oxydo-réduction chimiquement liés, les structures d'oxydoréduction.Dans le chapitre 3, des molécules modèles de graphène ont été sélectionnés afin de déterminer les conditions optimales de réaction entre graphène et tétrazine dérivés. Toutes les molécules de tétrazine ont d'abord été étudiés par électrochimie et ensuite mis à réagir avec le graphène par la demande électronique inverse Diels-Alder (DAinv) réaction dans un réacteur à micro-ondes, la XPS a été réalisée pour étudier sa composition chimique et de prouver la modification avec succès du graphène. Ensuite, le matériau de graphène tétrazine fonctionnalisé a été appliqué sur une électrode en acier inoxydable et ses performances électrochimiques ont été évaluées par voltamétrie cyclique et les tests de charge-décharge. La plupart des tétrazine modifié matériaux de graphène a montré de très bonnes performances électrochimiques et une faible résistance due à une bonne accessibilité des ions, ce qui en fait l'un des matériaux d'électrodes les plus prometteuses pour les supercondensateurs jusqu'à présent. Dans le chapitre 4, polypyrrole (PPy)-graphène nanocomposites ont été synthétisés par polymérisation de PPy sur les feuilles de graphène fonctionnalisés par tétrazine. Le matériau de graphène modifié contient des unités pyridazine tel que démontré par XPS. Puis PPy a été déposé sur ce matériau de graphène fonctionnalisé soit par polymérisation chimique ou électrochimique. Cellules de pièces symétriques ont été faites pour mesurer la capacité dans une configuration à deux électrodes. Les nanocomposites de polypyrrole-graphène avec 40% PPy présentent les meilleures performances électrochimiques et une faible résistance en raison d'une bonne accessibilité des ions, ce qui en fait l'un des meilleurs matériaux d'électrodes pour supercapacitor jusqu'à présent. / Graphene and graphene oxide based materials have attracted great attention since its discovery. However, as graphene sheet has a high specific surface area, it tends to form an irreversible agglomerates or even restack to form graphite through π–π stacking and van-der Waals interactions. Modifications need to be done to separate graphene sheets without bringing too much damage in its aromatic structure.In this thesis, two methods have been introduced to do the modification of graphene, nucleophilic substitution reaction for graphene oxide with a C/O~2 (FGS2), while inverse electron demand Diels-Alder reaction for graphene oxide with a very low oxygen content C/O~20 (FGS20). As in the latter case, tetrazine functionalized FGS20 has excellent conductivity, it has been further combined with polypyrrole to fabricate supercapacitor material.In chapter 2, we have covalently grafted tetrazine derivatives to graphene oxide through nucleophilic substitution. Since the tetrazine unit is electroactive and nitrogen-rich, with a reduction potential sensitive to the type of substituent and degree of substitution, we used electrochemistry and X-ray photoelectron spectroscopy to demonstrate clear evidence for grafting through covalent bonding. Chemical modification was supported by Fourier transform infrared spectroscopy and thermal analysis. Tetrazines grafted onto graphene oxide displayed different mass losses compared to unmodified graphene and were more stable than the molecular precursors. Finally, a bridging tetrazine derivative was grafted between sheets of graphene oxide to demonstrate that the separation distance between sheets can be maintained while designing new graphene-based materials, including chemically bound, redox structures.In chapter 3, model molecules of graphene were selected to determine the optimal reaction conditions between graphene and tetrazine derivatives. All tetrazine molecules were firstly studied by electrochemistry and then reacted with graphene through inverse electron demand Diels-Alder (DAinv) reaction in microwave reactor, X-ray photoelectron spectroscopy was carried out to study its chemical composition and prove the successfully modification of graphene. Then the tetrazine functionalized graphene material was coated on a Stainless Steel electrode and its electrochemical performances were assessed by cyclic voltammetry and charge-discharge experiments. Most of the tetrazine modified graphene materials showed very good electrochemical performance and a small resistance due to a good ion accessibility, which makes it one of the most promising electrode materials for supercapacitors so far.In chapter 4, polypyrrole (PPy)-graphene sheet nanocomposites have been synthesized by both chemical and in situ electrochemical polymerization of PPy on tetrazine derivatives functionalized graphene sheets. The modified graphene material contains pyridazine units as demonstrated by XPS. Then PPy was deposited on this functionalized graphene material either by chemical or electrochemical polymerization. Symmetrical coin cells were made to measure the capacitance in a two-electrode configuration. Polypyrrole-graphene nanocomposites with 40% PPy show the best electrochemical performances, with a very large capacitance per weight (326 F g-1 at 0.5 A g-1 and 250 F g-1 at 2 A g-1) and a small resistance due to a good ion accessibility, which makes it one of the best electrode materials for supercapacitors so far.

Thesis advisor: Zhifeng Ren / Silicon germanium alloys (SiGe) have long been used in thermoelectric modules for deep-space missions to convert radio-isotope heat into electricity. They also hold promise in terrestrial applications such as waste heat recovery. The performance of these materials depends on the dimensionless figure-of-merit ZT (= S2σ T/ κ), where S is the Seebeck coefficient, σ the electrical conductivity, κ the thermal conductivity, and T is the absolute temperature. Since 1960 efforts have been made to improve the ZT of SiGe alloys, with the peak ZT of n-type SiGe reaching 1 at 900 - 950 C. However, the ZT of p-type SiGe has remained low. Current space-flights run on p-type materials with a peak ZT ~ 0.5 and the best reported p-type material has a peak ZT of about 0.65. In recent years, many studies have shown a significant enhancement of ZT in other material systems by utilizing a nanostructuring approach to reduce the thermal conductivity by scattering phonons more effectively than electrons. Here we show, using a low-cost and mass-production ball milling and direct-current induced hot press compaction nanocomposite process, that a 50% improvement in the peak ZT, from 0.65 to 0.95 at 800 - 900C is achieved in p-type nanostructured SiGe bulk alloys. The ZT enhancement mainly comes from a large reduction in the thermal conductivity due to the increased phonon scattering at the grain boundaries and crystal defects formed by lattice distortion, with some contribution from the increased electron power factor at high temperatures. Moreover, nanocomposite approaches have been used to study the thermoelectric properties of other material systems such as bismuth telluride (Bi-Te), bismuth antimony (Bi-Sb), and half-Heusler phases. We observed a significant improvement in peak ZT of nanostructured p- and n-type half-Heusler compounds from 0.5 to 0.8 and 0.8 to 1.0 respectively. The ZT improvement is mainly due to the reduction of thermal conductivity. This nanostructure approach is applicable to many other thermoelectric materials that are useful for automotive, industrial waste heat recovery, space power generation, or solar power conversion applications. / Thesis (PhD) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Thesis advisor: Zhifeng Ren / Thermoelectric materials have attracted a lot of research interests because of their promising applications in solid-state cooling and power generation. The low ZTs of the current available thermoelectric materials have restricted the device efficiency, and thus the wide application of the thermoelectric technique. We propose a nanocomposite approach to improve ZT by reducing lattice thermal conductivity. The nanocomposite approach was first applied to n-type Si. Since there is no point defect scattering from Ge in pure Si, hence it provides an opportunity to study the scattering of grain boundaries. We found that the thermal conductivity is reduced by a factor of 10 in nanostructured Si in comparison with bulk crystalline Si. By adding 5 at% Ge, the thermal conductivity is further reduced by a factor of 2, thereby leading to a thermoelectric figure of merit 0.95 for Si95Ge5, similar to that of large grained Si80Ge20 alloys. Moreover, thermoelectric properties of In4Se3-x and Zn4Sb3 were investigated. Extremely low thermal conductivity values of 0.41 and 0.69 Wm-1K-1 were obtained in In4Se2.2 and Zn4Sb3 nanocomposites respectively, leading to peak ZTs of 1 and 1.3. / Thesis (PhD) — Boston College, 2011. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Hospital-acquired infections are a significant contributor to clinically-related morbidity and mortality. The majority of these infections are associated with the use of invasive medical devices, where urinary catheters account for ~36% of cases. Current preventative strategies have shown short-term (<7 days) success, however their long-term (>28 days) efficacy is unclear. This thesis explores the use of solution-cast polyurethane nanocomposite (PUNC) materials for antimicrobial drug delivery in urinary applications. It is hypothesised that the enhanced barrier properties of PUNCs, afforded by the incorporation of well-dispersed nanoinclusions, would allow for the sustained release of an antimicrobial agent. The objectives of this research were to investigate the antibacterial, mechanical and barrier properties of PUNCs incorporating various silicates modified using antimicrobials, hypothesised to also act as dispersing agents. Organically modified silicates (OMS) were prepared at 110%, 200% and 300% cationic exchange capacity (CEC) using the biocide, chlorhexidine diacetate (CHX), which was hypothesised to perform the dual functions; dispersant and antibacterial agent. Resulting OMS were incorporated at 1wt% and 5wt% loadings into a PU matrix to produce PUNCs; PEU-CHX1.1MMT, PEU-CHX2.0MMT, and PEU-CHX3.0MMT, respectively. CHX performed well as a dispersant, producing intercalated to partially exfoliated PUNCS. Antibacterial activity was dependent on OMS type and loading. PEU-CHX1.1MMT materials had poor antibacterial properties, but the addition of free CHX into the materials significantly improved their efficacy, demonstrating long-term sterility in an in vitro urinary tract (UT) model. PEU-CHX2.0MMT and PEU-CHX3.0MMT at 5wt% OMS loadings had partially exfoliated structures and excellent antibacterial activity. Cytotoxicity was evident in all materials, although to a lesser extent in the latter. Overall, intermediate OMS loadings of CHX2.0MMT would be expected to produce PUNCs with favourable antibacterial activity and cytocompatibility. PUNC drug-release profiles demonstrated sustained release compared to pristine PU, indicative of enhanced barrier properties. Their ultimate tensile properties decreased with increased OMS loading or addition of free CHX.Higher cationic-exchanged OMS caused significant reductions in strain. Young's modulus increased in response to higher %CEC OMS and loading. PUNCs show promise as antibacterial biomaterials for long-term urinary applications, where antimicrobial release and mechanical properties can be modulated through organic modification and OMS loading.

The focus of this work was to understand the fundamental dispersion mechanism of cellulose based nanofibers in bionanocomposites. The cellulose nanofibers were extracted from soybean pod and hemp fibers by chemo-mechanical treatments. These are bundles of cellulose nanofibers with a diameter ranging between 50 to 100 nm and lengths of thousands of nanometers which results in very high aspect ratio. In combination with a suitable matrix polymer, cellulose nanofiber networks show considerable potential as an effective reinforcement for high quality specialty applications of bio-based nanocomposites. Cellulose fibrils have a high density of –OH groups on the surface, which have a tendency to form hydrogen bonds with adjacent fibrils, reducing interaction with the surrounding matrix. The use of nanofibers has been mostly restricted to water soluble polymers. This thesis is focused on synthesizing the nanocomposite using a solid phase matrix polypropylene (PP) or polyethylene (PE) by hot compression and poly (vinyl alcohol) (PVA) in an aqueous phase by film casting. The mechanical properties of nanofiber reinforced PVA film demonstrated a 4-5 fold increase in tensile strength, as compared to the untreated fiber-blend-PVA film. It is necessary to reduce the entanglement of the fibrils and improve their dispersion in the matrix by surface modification of fibers without deteriorating their reinforcing capability. Inverse gas chromatography (IGC) was used to explore how various surface treatments would change the dispersion component of surface energy and acid-base character of cellulose nanofibers and the effect of the incorporation of these modified nanofibers into a biopolymer matrix on the properties of their nano-composites. Poly (lactic acid) (PLA) and polyhydroxybutyrate (PHB) based nanocomposites using cellulose nanofibers were prepared by extrusion, injection molding and hot compression. The IGC results indicated that styrene maleic anhydride coated and ethylene-acrylic acid coated fibers improved their potential to interact with both acidic and basic resins. From transmission electron micrograph, it was shown that the nanofibers were partially dispersed in the polymer matrix. The mechanical properties of the nanocomposites were lower than those predicted by theoretical calculations for both nanofiber reinforced biopolymers.

The focus of this work was to understand the fundamental dispersion mechanism of cellulose based nanofibers in bionanocomposites. The cellulose nanofibers were extracted from soybean pod and hemp fibers by chemo-mechanical treatments. These are bundles of cellulose nanofibers with a diameter ranging between 50 to 100 nm and lengths of thousands of nanometers which results in very high aspect ratio. In combination with a suitable matrix polymer, cellulose nanofiber networks show considerable potential as an effective reinforcement for high quality specialty applications of bio-based nanocomposites. Cellulose fibrils have a high density of –OH groups on the surface, which have a tendency to form hydrogen bonds with adjacent fibrils, reducing interaction with the surrounding matrix. The use of nanofibers has been mostly restricted to water soluble polymers. This thesis is focused on synthesizing the nanocomposite using a solid phase matrix polypropylene (PP) or polyethylene (PE) by hot compression and poly (vinyl alcohol) (PVA) in an aqueous phase by film casting. The mechanical properties of nanofiber reinforced PVA film demonstrated a 4-5 fold increase in tensile strength, as compared to the untreated fiber-blend-PVA film. It is necessary to reduce the entanglement of the fibrils and improve their dispersion in the matrix by surface modification of fibers without deteriorating their reinforcing capability. Inverse gas chromatography (IGC) was used to explore how various surface treatments would change the dispersion component of surface energy and acid-base character of cellulose nanofibers and the effect of the incorporation of these modified nanofibers into a biopolymer matrix on the properties of their nano-composites. Poly (lactic acid) (PLA) and polyhydroxybutyrate (PHB) based nanocomposites using cellulose nanofibers were prepared by extrusion, injection molding and hot compression. The IGC results indicated that styrene maleic anhydride coated and ethylene-acrylic acid coated fibers improved their potential to interact with both acidic and basic resins. From transmission electron micrograph, it was shown that the nanofibers were partially dispersed in the polymer matrix. The mechanical properties of the nanocomposites were lower than those predicted by theoretical calculations for both nanofiber reinforced biopolymers.

For more than a decade nanomaterials have attained huge attraction owing to the exceptionally different and excellent characteristics as compared to their bulk form. In the present research, we focus on understanding the properties and performance of nanocomposites in solid and liquid states. There are three major areas involved in this thesis research. Firstly, we will identify effective methods or techniques to evaluate nanomaterials. Conventional and non-conventional techniques will be implied. The second part is to study the interfacial reactions between nanoparticles (NPs) and fluid molecules. This is to obtain basic understanding of nanoparticles and their interactions with matrix materials. Thirdly, we will investigate the mechanical properties of nanocomposites. Experimental results showed that the mechanical properties of nanocomposites measured at macroscale exhibited differences when the shape and size of gold NPs were changed. The morphological characteristics of the material were shown effectively at the nanoscale based on the NPs' shape and size. The properties of NPs influenced the properties of gold colloid. Such changes were the result of the interfacial interaction of gold NPs and the host material.

Biobased polymers are a critical research topic as they may serve as replacement to traditional unsustainable petro-chemical polymers. It is vital to widen its range of applications by improving its physical and mechanical properties via light weighting and strength improvements. Light weighting can be accomplished by introducing foam morphology to the material while mechanical strength improvements can be achieved by inserting stiff filler material to the base polymer to form a composite. This study explores the physical, mechanical, thermal, rheological and morphological properties of blends, foams and composites between biobased PLA and PHBV matrix polymers and biobased chitin nanowhisker filler. It was found that foams produced from PLA and PHBV blends exhibits refined cellular morphology which leads to light weighting and good strength preservation while chitin nanowhiskers was determined to be a very effective filler for mechanical property improvements in both solid and porous materials.