No / Simply melt blended polypropylene/carbon nanotubes composites (PP/CNTs) usually present mechanical deterioration. In this work, multilayered sheet of PP/CNTs with improved tensile property was obtained by solid-phase orientation and hot compression. The initially blended PP/CNTs were highly orientated by employing a constrained slit die and hot compressed under a certain temperature and pressure by stacking eight layers together. The effects of compression temperature and pressure on the tensile property and AC conductivity of the multilayered sheets were examined to explore the evolution of hierarchical crystallization morphology and CNT networks. The multilayered sheet which was hot compressed at 184°C and 5 MPa demonstrated an optimum tensile strength of ∼132.5 MPa and an elongation at break ∼52.7%, respectively, raised by almost 3-fold compared with those initially blended PP/CNTs. By increasing compression temperature and decreasing pressure, the AC conductivity showed an increase of 2 to 4 orders of magnitude. / China Scholarship Council. Grant Number: 201806465028.

Composites are widely used in an increasing number of applications in diverse fields. However, most traditional composite materials are difficult to recycle. Because of their enhanced recyclability, thermoplastic single-polymer composites (SPCs), i.e., composites with fiber and matrix made from the same thermoplastic polymer, have attracted much attention in the recent years. High-performance polymer fibers in combination with same polymer matrices would lead to a fully recyclable single polymer composite that has major ecological advantages. However, because a single polymer is involved in the composite, thermoplastic SPCs manufacturing presents a unique set of technical problems, and different approaches from those in standard composites manufacturing are frequently needed. Two specific issues in SPCs manufacturing are how to produce distinct forms of the same polymer and how to consolidate them. So far, most investigations have been reported on a single-component hot compaction method and two-component molecular methods. However, in these methods, either the processing window is too narrow or some impure materials are introduced into the system. The key issue in thermoplastic SPCs processing is how to melt-process the matrix without significantly annealing or even melting the fiber. To overcome the above drawbacks in existing SPCs processing, particularly to widen the SPCs processing temperature window and to purify the SPCs, a novel SPCs manufacturing process utilizing the characteristics of slowly crystallizing polymers was developed and investigated. Highly oriented and highly crystalline fibers made of a slowly crystallizing polymer are mixed with the amorphous form of the same polymer and then consolidated together under heat and pressure. In this dissertation research, two slowly crystallizing polymers, poly(ethylene terephthalate) (PET) and poly(lactic acid) (PLA), were used as model systems for SPCs processing.. To study the deformation and failure mechanisms of PET and PLA SPCs, the SPCs were characterized using tensile test, tearing test, impact test, SEM, optical microscopy, and other methods. The change of crystallinity and orientation of the material forms during SPCs processing were characterized by DSC and XRD. The effects of major process conditions on the performance of the SPCs were studied. It was found that the processing temperature played a profound role in affecting the fiber-matrix bonding property. The compression molded SPCs exhibited enhanced mechanical properties. For the PET SPCs with 45% by weight fiber content the tensile strength is four folds of that of non-reinforced PET. After reinforcement, the tearing strength of the PLA SPCs is almost an order higher than that of the non-reinforced PLA. The fusion bonding behavior of two crystallizable amorphous PET sheets was also studied. Several characterization methods including SEM, TEM and polarized microscopy (either on etched or on non-etched samples) were used to observe interfacial bonding morphology of the crystallizable amorphous PET sheets. For a bonded sample, a layer of transcrystals with a thickness of 1-2 Ým was found right at the interface. A secondary but much larger zone with a distinct morphology was observed outside the transcrystal layer. With increase of the heating time, the width of the whole interfacial region decreases. The interfacial morphology was found to significantly affect the interfacial bonding quality. The testing results further indicated that high bonding temperature with an appropriate holding time promotes interfacial bonding of two crystallizable amorphous PET.

Le poly(acide lactique), PLA, est un polymère biocompatible et biodégradable, qui peut être produit à partir de ressources renouvelables. En conséquence, il a soulevé une attention toute particulière en tant que remplacement éventuel des polymères à base de pétrole. C’est un polyester aliphatique ayant des propriétés telles que module élevé, haute résistance, biocompatibilité et est donc un matériau prometteur pour diverses applications telles que les implants, l’encapsulation de médicaments et l'emballage. A cause de sa faible température de transition vitreuse, le PLA a une faible résistance thermique et les applications sont donc limitées à celles qui ne sont pas associées à des températures élevées. En outre, ce polymère souffre d'un faible degré de cristallinité. L'augmentation du taux de cristallinité dans de nombreuses techniques de mise en forme, telles que le moulage par injection, est nécessaire. Il y a plusieurs façons d'augmenter le niveau de cristallinité du PLA. Ces procédés comprennent l'utilisation d'agents nucléants, de plastifiants, ou de combinaisons d'agents plastifiants et de nucléation. La cristallisation du PLA à l'état fondu se présente sous deux formes cristallines légèrement différentes connues sous les noms α et α'. Cette étude compare la capacité d'auto-nucléation de ces deux formes cristallines par auto-nucléation. Ceci est réalisé en comparant les températures de cristallisation lors du refroidissement des échantillons préalablement cristallisés à diverses températures, puis de nouveau chauffé à une température dans la plage de fusion partielle du PLA. Dans la deuxième étape, l'effet des paramètres cinétiques et le poids moléculaire du PLA sur l'efficacité de nucléation des PLA phases cristallines a été étudié. Cette partie de l’étude ouvre une nouvelle voie pour comprendre le rôle des modifications cristallines du PLA qui mènent aux conditions optimales pour la cristallisation du PLA. La mise en forme des polymères implique des contraintes de cisaillement et d’élongation, ce qui implique une cristallisation induite par l’écoulement et la solidification qui s’en suit. Les propriétés mécaniques des produits finals dépendent du degré de cristallisation et de la nature des cristaux formés. Par conséquent, l'optimisation du procédé nécessite une bonne compréhension de la façon dont l’écoulement influence la cristallisation. Le type d'écoulement peut jouer un rôle important sur la cristallisation. Par exemple, l'écoulement élongationnel provoque l’orientation et l’étirement des molécules dans le sens de l'extension, comme dans le cas de la mise en forme de fibres et le soufflage de film, en aidant le processus de cristallisation induite par l'écoulement. Une littérature abondante existe sur la ii cristallisation des thermoplastiques classiques induite par l'écoulement. Cela dit, moins d'attention a été accordée à l'effet de l'écoulement de cisaillement et d'allongement sur la cristallisation du PLA. Comme étudié dans la dernière partie de ce document, l'effet du poids moléculaire sur la cristallisation induite par cisaillement du PLA est rapporté. Pour cela, trois différents PLA à faible, moyen et haut poids moléculaire ont été préparés par réaction d'hydrolyse. Ensuite, en utilisant un rhéomètre oscillatoire, l’effet du cisaillement sur la cinétique de cristallisation du PLA a été examiné. / Abstract : Poly(lactic acid), PLA, is a biocompatible and biodegradable polymer that can be produced from renewable resources. As a result, it has raised particular attention as a potential replacement for petroleum-based polymers. It is an aliphatic polyester with properties such as high modulus, high strength, and biocompatibility and is thus a promising material for various applications such as implants, drug encapsulation, and packaging. In the wake of low glass transition temperature, PLA has a low heat resistance and its application is limited to those not associated with high temperatures. In addition, this polymer suffers from a low degree of crystalinity. Increasing the crystallization rate in many processing operations, such as injection molding, is required. So far, many routes have been found to improve the crystallinity of PLA. These methods include using nucleating agents, plasticizers, and combination of nucleating agents and plasticizers together. PLA crystallization in the melt state results in two slightly different crystalline forms known as α and α’forms. This thesis compares the self-nucleation ability of these two crystal forms by self-nucleation. This is achieved by comparing crystallization temperatures upon cooling for samples previously crystallized at various temperatures and then re-heated to a temperature in the partial melting range for PLA. In the second step, we study the effect of molecular weight of PLA on the nucleation efficiency of PLA crystalline phases. This part of the investigation opens a new pathway to understand the role of PLA crystalline phases on the optimal condition for its crystallization kinetics. Polymer processing operations involve mixed shear and elongational flows and cause polymer molecules to experience flow-induced crystallization during flow and subsequent solidification. The mechanical properties of the final products are significantly dependent upon the degree of crystallization and types of formed crystals. Therefore, optimization of any polymer process requires a good understanding of how flow influences crystallization. The type of flow can play a significant role in affecting crystallization. For example, elongational flow causes molecules to orient and stretch in the direction of extension, as in the case of fiber spinning and film blowing, helping the process of flow-induced crystallization. An extensive body of literature exists on flow-induced crystallization of conventional thermoplastics. Having said that, less attention has been paid to the effect of shear and elongational flow on the PLA crystallization kinetics. As investigated in the final part of this thesis, the effect of iv molecular weight on the shear-induced crystallization of PLA is reported. For this, low, medium and high molecular-weight PLAs were prepared from a high molecular weight one by a hydrolysis reaction. Next, by means of a simple rotational rheometry, effect of the shear flow was examined on the crystallization kinetics of these three PLAs.

No description available.

No description available.

Master of Science / Mercury is the most mysterious planet in the inner Solar System, suggested by observations from the MESSENGER mission. These observations shine a light on potential processes occurring within Mercury as it evolved over time. Scientific instruments aboard MESSENGER indicate that Mercury has a very thin surface layer of broken rocks, a thin crustal layer covered by lavas erupted from a melt formed in a relatively thin, FeO poor mantle, and a large metal rich core made from Fe and some quantity of a light element. These conditions are different than those seen on Earth: a thick crust covered by a layer of varied thickness made up of loose unconsolidated rocks and dust, a large mantle with more FeO, and a smaller core to planet ratio. To understand how these non-Earth like conditions affect how the planet's interior changes with time, a modified evolution model was created to track the changes in heat and chemistry within Mercury. This model accounts for complications like a dynamic core density that changes with a growing inner core, the formation method of the inner core, and the FeO poor mantle composition. Using this model offers illumination on the conditions Mercury experienced after it formed. This model is limited, but results suggest that Mercury's mantle began at an initial mantle temperature of 1600 K, and a mantle reference viscosity of 1021–1022 Pa s, indicating the mantle was less likely to flow easily. Model results also suggest the core contained some sulfur from 0.05–8.9 wt.% S, derived from the MESSENGER data. BepiColombo, a new Mercury mission, will provide some perspectives on the interior of Mercury, leading to more detailed information about conditions present after planetary formation and the effect of non-Earth like conditions on a planet's interior as it cools.

The purpose of the work described in this thesis was to explore the use of fractional crystallization as a technology that can be used to separate medium-curie waste from the Hanford Site tank farms into a high-curie waste stream, which can be sent to a Waste Treatment and Immobilization Plant (WTP), and a low-curie waste stream, which can be sent to Bulk Vitrification. The successful semi-batch crystallization of sodium salts from two single shell tank simulant solutions (SST Early Feed, SST Late Feed) demonstrated that the recovered crystalline product met the purity requirement for exclusion of cesium, sodium recovery in the crystalline product and the requirement on the sulfate-to-sodium molar ratio in the stream to be diverted to the WTP. In this thesis, experimental apparatus, procedures and results are given on scaled-down experiments of SST Early Feed for hot-cell adaptation along with operating parameters and crystallization mechanism studies on early feed multi-solute crystallization. Moreover, guidance is given regarding future steps towards adapting the technology to multi-salt crystallization kinetic parameter estimates and modeling. Crystallization, Evaporative Fractional Crystallization, Nuclear Waste Pretreatment, Cesium Removal, Hanford, SST Early and Late feed, Multi-solute, Multi-salts, Simulant Testing

Combinatorial techniques have changed the paradigm of materials research by allowing a faster data acquisition in complex problems with multidimensional parameter space. The focus of this thesis is to demonstrate biomaterials design and characterization via preparation of two dimensional combinatorial libraries with chemically-distinct structured patterns. These are prepared from blends of biodegradable polymers using thickness and temperature gradient techniques. The desired pattern in the library is chemically-distinct cell adhesive versus non-adhesive micro domains that improve library performance compared to previous implementations that had modest chemical differences. Improving adhesive contrast should minimize the competing effects of chemistry versus physical structure. To accomplish this, a method of blending and crosslinking cell adhesive poly(季aprolactone) (PCL) with cell non-adhesive poly(ethylene glycol) (PEG) was developed. We examine the interaction between MC3T3-E1 osteoblast cells and PCL-PEG libraries of thousands of distinct chemistries, microstructures, and roughnesses. These results show that cells grown on such patterned biomaterial are sensitive to the physical distribution and phases of the PCL and PEG domains. We conclude that the cells adhered and spread on PCL regions mixed with PEG-crosslinked non-crystalline phases. Tentatively, we attribute this behavior to enhanced physical, as well as chemical, contrast between crystalline PCL and non-crystalline PEG.

La cristallisation est un processus d’auto-assemblement de molécules à partir d’une phase désordonnée (liquide, amorphe ou gazeuse). De façon générale, la miscibilité à l’état solide entre un constituant d’intérêt et son impureté dépendent d’une part, de la structure moléculaire de ces deux espèces, et d’autre part, de la structure cristalline du réseau hôte, c’est-à-dire celui du composé d’intérêt. En cas d’absence de miscibilité, l’optimisation des conditions de cristallisation permet un retrait total de l’impureté du composé visé. Cette thèse vise à démontrer que, lorsque deux molécules sont semblables et que leur structure cristalline est peu dense, des solutions solides de substitutions peuvent se former et empêcher le retrait de l’impureté de l’espèce cible. Inversement, lorsque les impuretés sont très diférentes de l’espèce à purifer, l’absence de solution solide est observée et permet leur élimination totale grâce à une bonne discrimination à l’état solide. Le système du phénanthrène, un composé servant entre autres de base pour la synthèse de composésmorphiniques, a été choisi pour illustrer cette thèse. Diverses méthodes de cristallisation (fusion de zone, co-cristallisation, recristallisation en solution, sublimation-condensation) ont été testées et ont permis, après optimisation et combinaison, l’obtention à l’échelle préparative de phénanthrène pur à plus de 99,999 % en moles, ce qui le place sur l’échelle de l’ultra-pureté (pureté > 99,9 % en moles). / Crystallization is a process during which molecules self assembly from a disordered (liquid, amorphous or gaseous) phase. The miscibility in the solid state between a component of interest and its impurity depends on: (i) their molecular structures, (ii) the crystal structure of the host lattice (namely, that of the component of interest). When no solid solution exists, the impurity can be completely eliminated from the target product after optimization of the crystallization conditions.The present thesis intends to demonstrate that, when two compounds present similar molecular structures with low-density crystal structures, solid solution formation can occur which prevents from their complete separation. Conversely, in case of sufcient dissimilarity, no solid solution is stable and their separation is possible thanks to a large discrimination in the solid state. The phenanthrene system – a model compound used as base for the synthesis of morphine derivatives – was chosen to illustrate this thesis. Several crystallization methods (zone melting, co-crystallization, solvent assisted crystallization and sublimation-condensation) were investigated and permitted, after optimization and combination, to obtain 99.999(9) mole % purity phenanthrene (which is above the ultrapure grade of 99.9 mole %).

No description available.