abstract: Nanoporous materials, with pore sizes less than one nanometer, have been incorporated as filler materials into state-of-the-art polyamide-based thin-film composite membranes to create thin-film nanocomposite (TFN) membranes for reverse osmosis (RO) desalination. However, these TFN membranes have inconsistent changes in desalination performance as a result of filler incorporation. The nano-sized filler’s transport role for enhancing water permeability is unknown: specifically, there is debate around the individual transport contributions of the polymer, nanoporous particle, and polymer/particle interface. Limited studies exist on the pressure-driven water transport mechanism through nanoporous single-crystal nanoparticles. An understanding of the nanoporous particles water transport role in TFN membranes will provide a better physical insight on the improvement of desalination membranes. This dissertation investigates water permeation through single-crystal molecular sieve zeolite A particles in TFN membranes in four steps. First, the meta-analysis of nanoporous materials (e.g., zeolites, MOFs, and graphene-based materials) in TFN membranes demonstrated non-uniform water-salt permselectivity performance changes with nanoporous fillers. Second, a systematic study was performed investigating different sizes of non-porous (pore-closed) and nanoporous (pore-opened) zeolite particles incorporated into conventionally polymerized TFN membranes; however, the challenges of particle aggregation, non-uniform particle dispersion, and possible particle leaching from the membranes limit analysis. Third, to limit aggregation and improve dispersion on the membrane, a TFN-model membrane synthesis recipe was developed that immobilized the nanoparticles onto the support membranes surface before the polymerization reaction. Fourth, to quantify the possible water transport pathways in these membranes, two different resistance models were employed. The experimental results show that both TFN and TFN-model membranes with pore-opened particles have higher water permeance compared to those with pore-closed particles. Further analysis using the resistance in parallel and hybrid models yields that water permeability through the zeolite pores is smaller than that of the particle/polymer interface and higher than the water permeability of the pure polymer. Thus, nanoporous particles increase water permeability in TFN membranes primarily through increased water transport at particle/polymer interface. Because solute rejection is not significantly altered in our TFN and TFN-model systems, the results reveal that local changes in the polymer region at the polymer/particle interface yield high water permeability. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2018

Puisque cette thèse présente deux études indépendantes sur les nanocristaux de cellulose, le résumé a été divisé en deux sections qui font référence aux chapitres II et III, respectivement.Investigation morphologique et structurelle des nanocristaux de cellulose I et II préparés par hydrolyse à l'acide sulfuriqueLe but du travail de recherche présenté dans le chapitre II était de produire, de caractériser et de comparer les CNC obtenus à partir de la pâte de bois d'eucalyptus en utilisant trois méthodes différentes: i) l'hydrolyse classique à l'acide sulfurique (CN-I), ii) l'hydrolyse acide de la cellulose précédemment mercerisée par traitement alcalin (MCN-II), et iii) la solubilisation de la cellulose dans l'acide sulfurique et la recristallisation subséquente dans l'eau (RCN-II). Les trois types de CNC préparés présentent des morphologies et des structures cristallines différentes. Lorsque les conditions d'hydrolyse acide sont mises en place de telle sorte que les domaines cristallins dans la pâte de bois initial et la cellulose mercerisée (WP et MWP, respectivement) sont préservés (60 wt% H2SO4, 45°C, 50 min), les nanocristaux résultants conservent la nature fibrillaire des fibres d’origine (c'est-à-dire que l'axe de la chaîne est parallèle au grand axe des particules aciculaires) et leur type allomorphe initial (I pour WP et II pour la MWP). Dans les deux cas, les particules sont principalement composées de quelques cristallites élémentaires liées latéralement. Les nanocristaux unitaires dans les CNC préparés à partir de cellulose mercerisée (MCN-II) sont plus courts, mais plus larges que ceux préparés à partir des fibres de cellulose I (CN-I). Si des conditions plus sévères sont considérées (64 wt% H2SO4, 40°C, 20 min), ce qui entraîne la dépolymérisation et la dissolution de la cellulose native, les chaînes courtes recristallisent en rubans de Cell-II lors de la régénération dans l'eau à température ambiante. Dans ces rubans tortueux, l'axe de la chaîne serait perpendiculaire au grand axe du nanocristal et parallèle à son plan basal.La structure moléculaire et cristalline unique des nano-rubans implique qu'un nombre plus élevé d'extrémités de chaîne réductrice sont situées à la surface des particules, ce qui peut être important pour des modifications chimiques subséquentes et pour de potentielles applications spécifiques telles que la biodétection et la bio-imagerie. Donc, cette étude permet de mieux comprendre la structure cristalline et la morphologie de la CNC obtenue par régénération à l'acide sulfurique.Propriétés mécaniques de nanocomposites de caoutchouc naturel renforcé avec des nanocristaux de cellulose à facteur de forme élevé extraits de la coque de sojaDans cette étude, les CNCs ont été isolés des coques de soja à partir d’un traitement par hydrolyse avec de l'acide sulfurique. Ces CNCSH ont été utilisés comme phase de renfort dans une matrice NR par casting à différents taux de charge, à savoir 1, 2.5 et 5% en poids. Les effets des CNCSH sur la structure ainsi que sur les propriétés thermiques et mécaniques du NR ont été étudiés. Par exemple, en ajoutant seulement 2,5% en poids de CNC, le module de conservation en traction du nanocomposite à 25 °C est environ 21 fois plus élevé que celui de la matrice NR non chargée. Cet effet de renfort est supérieur à celui observé pour les CNCs extraits d'autres sources. Il peut être attribué non seulement au facteur de forme élevé de ces CNCs, mais aussi à la rigidité du réseau percolant de nanoparticules formé au sein de la matrice polymère. De plus, il a été constaté que la sédimentation des CNC pendant la mise en œuvre du film nanocomposite par casting joue un rôle crucial sur les propriétés mécaniques. Une contribution importante de ce travail est de mettre en évidence l'importance de la sédimentation des CNCs, pendant l'étape d'évaporation sur les propriétés mécaniques des nanocomposites, ce qui est rarement mentionné dans la littérature. / Since this thesis presents two independent studies on cellulose nanocrystals, the abstract was divided in two sections referring to chapters II and III, respectively.Comprehensive morphological and structural investigation of cellulose I and II nanocrystals prepared by sulfuric acid hydrolysisCellulose nanocrystals (CNCs) were produced from eucalyptus wood pulp using three different methods: i) classical sulfuric acid hydrolysis (CN-I), ii) acid hydrolysis of cellulose previously mercerized by alkaline treatment (MCN-II), and iii) solubilization of cellulose in sulfuric acid and subsequent recrystallization in water (RCN-II). The three types of CNCs exhibited different morphologies and crystal structures that were characterized using complementary imaging, diffraction and spectroscopic techniques. CN-I corresponded to the type I allomorph of cellulose while MCN-II and RCN-II corresponded to cellulose II. CN-I and MCN-II CNCs were acicular particles composed of a few laterally-bound elementary crystallites. In both cases, the cellulose chains were oriented parallel to the long axis of the particle, although they were parallel in CN-I and antiparallel in MCN-II. RCN-II particles exhibited a slightly tortuous ribbon-like shape and it was shown that the chains lay perpendicular to the particle long axis and parallel to their basal plane. The unique molecular and crystal structure of the RCN-II particles implies that a higher number of reducing chain ends are located at the surface of the particles, which may be important for subsequent chemical modification. While other authors have described nanoparticles prepared by regeneration of short-chain cellulose solutions, no detailed description was proposed in terms of particle morphology, crystal structure and chain orientation. Was provide such a description in the present document.Mechanical properties of natural rubber nanocomposites reinforced with high aspect ratio cellulose nanocrystals isolated from soy hullsCellulose nanocrystals (CNCs) were isolated from soy hulls by sulfuric acid hydrolysis. The resulting CNCs were characterized using TEM, AFM, WAXS, elemental analysis and TGA. The CNCs have a high crystallinity, specific surface area and aspect ratio. The aspect ratio (around 100) is the largest ever reported in the literature for a plant cellulose source. These CNCs were used as a reinforcing phase to prepare nanocomposite films by casting/evaporation using natural rubber as matrix. The mechanical properties were studied in both the linear and non-linear ranges. The reinforcing effect was higher than the one observed for CNCs extracted from other sources. It may be assigned not only to the high aspect ratio of these CNCs but also to the stiffness of the percolating nanoparticle network formed within the polymer matrix. Moreover, the sedimentation of CNCs during the evaporation step was found to play a crucial role on the mechanical properties.

The main goal of this research is to construct hierarchical microstructures from polymer nanocomposites. Specifically, the research focused on constructing tensegrity-inspired microstructure where the nanoparticles are the compression members and the polymer matrix is tensile web. In order to achieve the tensegrity-inpired microstruture, the research was conducted with the following objectives. 1. Synthesis of Hydroxyapatite (HAp) nanoparticles of controlled shapes using block copolymer templates. 2. Investigation of the effects of particle loadings and shapes on isotropic nanocomposite properties. 3. Construction of HAp building blocks into the tensegrity-inspired microstructures First, in order to use the nanoparticles for this structure, needle-shaped HAp nanoparticles were synthesized using block copolymer templates. The results indicated that significant amount of polymer remained on particle surface. Since these particles were coated with polymer blocks, the decorated polymer blocks were considered as the interphase material which would be used to prestress the HAp nanoparticles, and the particles would be acted as the building blocks for constructing tensegrity-inspired microstructure. For nanocomposites, polymer coating on HAp nanoparticles promoted particle dispersion. The effect of particle shapes on thermomechanical properties did not show significant differences between the two particle systems due to their low aspect ratios and chemical similarity. However, the polymer crystallinity and crystallization showed different trend as a function of particle loadings in two particle systems, and the behavior was unified through a common particle spacing of approximately 120 nm. In order to investigate the effect of particle arrangement in the polymer matrix, needle-shaped HAp nanoparticles synthesized with two different block copolymers were mixed with different morphology of polymer matrices and manipulated particle arrangement using the drawing process. Nanocomposites prepared with different matrix morphologies showed the similar dispersion characteristics and reinforcement behavior. The experimental results showed the drawing process influenced the particle arrangement in the polymer matrix, and the particle arrangement and reinforcement behavior were influenced by polymer matrix morphology. The thermomechanical properties of both matrix systems enhanced through the drawing process in the glassy region, but the effect of degree of particle orientation was difficult to distinguish due to low aspect ratios of HAp particles which was not enough to impact on overall microstructure.

New approaches through grafting initiators onto the surface of inner-wall of mesoporous silica to synthesize polymer inside the nano-channels to obtain mesoporous silica/polymer nanocomposites were developed and investigated. Using the newly developed approach, PMMA was successfully synthesized through free radical polymerization and nylon 6 though in situ anionic ring-opening polymerization inside the nano-channels. The spherical mesoporous silica/PMMA composites we obtained showed a higher degradation temperature and narrower degradation range than pure commercially available PMMA. Spherical PMMA capsules were obtained after the silica network was dissolved with hydrofluoric acid, these pure PMMA spheres had the same thermal properties and morphology as they had with in the composites. The BMS/nylon 6 nanocomposites were spheres with the same diameter as pure BMS. About 50 wt% of the composites was newly synthesized nylon 6. The synthesized nylon 6 was proven to contain both α-form crystallite and γ-form crystallites with covalent bonds with the surface of silica inside the nano-channels.

Polymer nanocomposites (PNCs) have gained significant interest because they have outstanding performance that allows cost reduction, weight reduction, and product improvement. This research study focuses on the manufacture and characterization of PNCs in order to explore their potential in automotive applications. More specifically, polypropylene (PP) nanocomposites reinforced with xGnP and nanokaolin were fabricated by manufacturing methods that optimize their performances. Exfoliated graphite nanoplatelets (xGnP) are promising nanofillers that are cost effective and multifunctional with superior mechanical, thermo-mechanical and electrical properties. Nanokaolin is a newly introduced natural mineral mind in Georgia that has not been studied as of now. PNCs reinforced with these two nanofillers were characterized in terms of mechanical, thermo-mechanical, and various other properties, and then compared to talc- reinforced PP composites, which are the current state of the art for rear bumpers used by Honda Motor. Characterization results indicated that xGnP had better performance than talc and nanokaolin. Furthermore, the addition of xGnP introduces electrical conductivity in the PNCs, leading to more potential uses for PNCs in automotive applications such as the ability to be electrostatic painted. In order to fabricate PNCs with a desired conductivity value, there is need for a design tool that can predict electrical conductivity. Existing electrical conductivity models were examined in terms of model characteristics and parameters, and model predictions were compared to the experimental data. The percolation threshold is the most important parameter in these models, but it is difficult to determine experimentally, that is why a correlation between thermo-mechanical properties and electrical conductivity is also investigated in this study.

Polymer-nanoplatelet hybrid membranes show promise as the next generation of membranes, but in order to make these realizable, methods to produce these materials on a large scale are necessary. Some authors have successfully produced these types of gas separation membranes. Typically these reports have utilized melt blending and in situ polymerization. Few, however, have utilized solution blending for creating membranes via phase inversion (asymmetric membranes). And to date, there have not been any reports regarding the fabrication of asymmetric membranes containing nanoplatelet filler materials. In this work we have developed a solution-based procedure for the formation of hybrid polymer-nanoplatelet dopes for dense film and asymmetric hollow fiber membrane formation. Dense film membrane studies were used to prove the effectiveness of our exfoliation and dispersion process developed for this work. Permeation measurements showed the hybrid membranes have desirable transport properties that are on par with mathematical model predictions. Additionally, TEM characterization provided strong evidence supporting the efficacy of our preparation procedures to produce an exfoliated system of nanoplatelets. We also showed that these procedures are applicable to different polymer systems (cellulose acetate and Torlon) of commercial relevance. Demonstrating the successful production of dense films set the stage for asymmetric hollow fiber membrane formation. We report the first production of asymmetric hollow fiber membranes containing nanoplatelet fillers; indicating that the process can be applied in a realistic membrane formation platform. These accomplishments serve as the groundwork for future nanocomposite formation.

Two different interfaces were the focus of study: 1) the interface between disordered amorphous carbon and inorganic materials (metal nanostructures and silicon), and 2) the interface between partially ordered graphene (graphene oxide) and synthetic polymer matrix. Specifically, the uniqueness of this study can be summarized through the following novel findings, fabrication processes, and characterization techniques: • A simple and efficient process for faster, greener, less-expensive, and highly localized transformation of amorphous carbon nanostructures into graphitic nanostructures using low temperature heat and light treatments was developed for the fabrication of low-resistance interfaces between carbon nanomaterials and inorganic metal surfaces. • A new protocol for high resolution mapping the charge distribution and electronic properties of nanoscale chemically heterogeneous domains on non-homogeneous surfaces such as graphene oxide was established. • High strength laminated mechanical nanocomposites based on high interfacial stress transfer between polymer matrices and large area, flat, and non-wrinkled graphene oxide sheets were suggested and demonstrated. • Scanning Thermal Twist Microscopy – a thermal microscopy based technique was developed and demonstrated for characterizing the thermal properties of homogeneous and heterogeneous interfaces with nanoscale spatial resolution and high thermal sensitivity unachievable using traditional techniques.

Thesis (M.S.)--State University of New York at Binghamton, Thomas J. Watson School of Engineering and Applied Science, Department of Mechanical Engineering, 2009.. / Includes bibliographical references.

Thesis (Ph. D.)--State University of New York at Binghamton, Materials Science and Engineering Program, 2009. / Includes bibliographical references.

Le magnésium est le plus léger des métaux, ce qui lui confère un fort potentiel pour être utilisé dans des applications où l’allégement des structures est requis. Pour autant, sa résistance mécanique est très faible, et doit donc être augmentée afin de rivaliser avec d’autres métaux légers tels que l’aluminium ou le titane. Une solution consiste à renforcer le magnésium et ses alliages en introduisant des nanoparticules d’oxydes. De par sa structure cristalline hexagonale compacte, le magnésium présente des propriétés plastiques complexes telles qu’une très forte anisotropie plastique et une prédisposition au maclage. La compréhension de ces mécanismes de déformation est essentielle pour le développement de nanocomposites plus performants en vue d’une utilisation industrielle plus répandue. Dans ce travail, nous nous sommes intéressés à l'élaboration et à la caractérisation de nanocomposites de magnésium pur renforcés par des particules d’oxydes. Différentes techniques ont été testées pour l’élaboration des nanocomposites : la solidification assistée aux ultrasons et le procédé de friction malaxage. L’homogénéité de la dispersion des particules a été vérifiée en 2D par observations en microscopie électronique et également en 3D par tomographie aux rayons X. On montre ainsi que le procédé de friction malaxage permet d'obtenir une distribution homogène des particules, tout en réduisant leur taille. Des essais de traction ont permis de mettre en évidence une augmentation de la limité d’élasticité pour une fraction volumique aussi faible que 0.3 %. Afin d’isoler le rôle des particules de celui des joints de grains sur le comportement plastique du nanocomposite, nous avons réalisé des essais de micro-compression sur des micro-piliers monocristallins usinés par canon à ions focalisés (FIB) dans des échantillons ayant préalablement subis un traitement thermique favorisant la croissance anormale des grains. Différentes orientations cristallines et tailles de micro-piliers ont été testées en vue d'étudier l’influence des particules d’une part sur la plasticité dans le plan basal par mouvement de dislocations et d’autre part sur la déformation par maclage. Contre toute attente, les essais sur monocristaux favorablement orientés pour un glissement basal ne montrent pas l’effet durcissant observé macroscopiquement. Nous attribuons cet effet à la densité initiale de dislocations mobiles, plus importante dans les nanocomposites que dans le magnésium pur, du fait des concentrations de contraintes autour des particules. Ces densités initiales de dislocations mobiles tendent également à supprimer l'effet de taille classiquement observé dans le magnésium pur. Les particules modifient également le mécanisme de déformation par maclage en favorisant l’apparition simultanée de plusieurs macles dans le micro-pilier qui interagissent entre elles au cours de la déformation alors que les micro-piliers de magnésium pur présentent généralement une macle unique (dans certains cas deux) qui envahi tout le monocristal. Ces résultats constituent une contribution originale à la compréhension du rôle des nanoparticules dans la déformation plastique des monocristaux de nanocomposites à base de magnésium. / Magnesium is the lightest of all structural metals, which gives it a huge potential to be used in applications that require lightweighting. However, its strength needs to be increased in order to compete with other light metals such as aluminum and titanium. A solution is the reinforcement of magnesium and its alloys with the addition of oxide nanoparticles. The hexagonal close packed crystalline structure is responsible for the complex plasticity of magnesium, which is characterized by a very strong plastic anisotropy as well as a complex twinning activity. Understanding these deformation mechanisms is crucial for the development of more performant nanocomposites, allowing widespread industrial application. The present work focuses on the processing and characterization of magnesium based nanocomposites reinforced with oxide particles. Two different processing techniques have been compared: friction stir processing and ultrasound assisted casting. The homogeneity of the dispersion of the reinforcement particles has been verified in 2 and 3 dimensions using electron microscopy and X-ray tomography, respectively. Friction stir processing produces nanocomposites with a more homogeneous dispersion of particles, while reducing their size. Tensile tests have shown strengthening of magnesium with the addition of a volume fraction of only 0.3 % of reinforcement. An annealing heat treatment has then been performed in order to promote abnormal grain growth and single crystalline microcolumns for microcompression testing have been machined by focused ion beam (FIB). The purpose is to isolate the role of particles. The orientation dependent mechanism of deformation and the size effects have been studied in order to understand the influence of the reinforcement particles on the plasticity for orientations favorable for basal slip or tensile twinning. Differently from the strengthening observed macroscopically, no clear strengthening effect is observed on microcolumns when dislocation glide operates. The reason is the higher density of potentially mobile dislocations that is generated due to stress concentrations around the reinforcement particles. In addition, the size effects usually observed on pure magnesium have also been suppressed with the addition of particles. The reinforcement particles seem to affect the twin nucleation stress and twin morphology: particles induce the nucleation of multiple twins inside a microcolumn, whereas in pure magnesium, only one or two twins have been observed. These results provide relevant insights on the role of nanoparticles on the onset of plastic deformation, as well as size effect, in single crystalline magnesium nanocomposites.