Research is presented on the crystallization and melting behavior of an aromatic semi crystalline polyimide known as LaRC CPI - 2 (Langley Research Center Crystalline rolyimide - second generation). This aromatic polyimide, a structural variant of the well known LaRC CPI, is synthesized froml 1,4-bis( 4-aminophenoxy-4' -benzoyl)benzene (1,4-BABB) and 4,4' -oxydiphthalic dianhydride (ODPA). The multiple melting behavior at ca. 334°C and 364°C, characteristic of this polymer, is analyzed and explained. Transmission electron microscopy (TEM), wide angle X-ray diffraction (W AXD), and small angle X-ray scattering (SAXS) studies, in conjunction with differential scanning calorimetry (DSC) analysis, show that the high melting transition results from the melting of lamellae which were melt recrystallized during heating in a DSC. The effects of synthesis and process variables upon the crystallization and melting properties of this polyimide were also studied. The DSC response of LaRC CPI - 2 films and powders of varying molecular weight are compared and contrasted. Powders generally melt at a higher temperature than films of the same molecular weight. The glass transition temperature, T g' of both the powders and films are found to be dependent upon molecular weight. An interpolated value of T g for the infinite molecular weight LaRC CPI - 2 is ca. 234°e. In a study of the development of crystallinity in films during standard thermal imidization, crystallinity was found to initiate off the glass surface very early in the process leaving an amorphous layer at the air surface after the full thermal treatment. LaRC CPI - 2 powder 'types' synthesized in different solvents, dimethylacetamide (DMAc) and m-cresol present with dramatically different melting, melt stability and crystallization properties. Though the chemical architecture and crystal lattice structure are the same, the powders synthesized in DMAc display dual melting transitions at ca. 334°C and 364°C, while the powders from m-cresol melt singularly at ca. 409°C. Rheological analysis, along with annealing data, revealed a higher temperature melt stability in the powders from m-cresol. It is postulated that the differences in the properties of the two powders are the result of differing initial molecular weights and a suppression of a cross-linking ketimine reaction in the polymer produced in m-cresol. / Ph. D.

Yes / Extrusion-a unit operation in polymer processing has been in extensive use since the great age of plastic technology. It is a simple operation that enables within one equipment the sequential conveying of solid polymer chips or powder, their melting, mixing, pumping and shaping via a die into a variety of high tonnage and/or value products. Pipes, bottles, films are the most common examples but the list of applications is endless from tiny micromoulded parts to large structural profiles. Extrusion is not limited to plastics but is used hot or cold to process soft solids like food, industrial and pharmaceutical pastes, as well as metals and ceramics. Most of the advances in extrusion processing have concentrated in improving the essential functions of extrusion: solid conveying, melting, pumping and mixing. The literature abounds with descriptions of such advances pushing the limits of the extrusion in an incremental way. In this paper, we describe step-changes in enhancing extrusion, which opens up new applications to better old technology-make them safer, cheaper and cleaner. The new designs presented in this paper have also the potential to develop new reactor technology for viscous fluids.

The Cortlandt Complex in New York is a composite intrusion of six mafic plutons and contains pelitic xenoliths that experienced extensive interaction with Mg-rich basaltic melt. The complex is an excellent natural example of ultra-high temperature (UHT) metamorphic processes and country rock-magma interaction due to mappable units of hybrid igneous rocks and the presence of large, partially melted, politic "emery" xenoliths. Previous attempts to understand the formation of the UHT xenoliths in the Cortlandt have provided the petrologic foundation for more rigorous thermodynamic modeling to determine the petrogenesis of these materials and to ultimately contribute to the understanding of UHT metamorphism in the Earth's crust. This work focuses on the development of hybrid monzonorites and emery at Salt Hill, located in the southeasternmost edge of the Cortlandt Complex. First, a thermobarometric study focuses on the P-T conditions of the country rock into which the Complex intruded. Pelitic schists from contact aureoles around a nearby pluton chemically and chronologically related to the complex, record high-P (~ 0.9 GPa, ~ 32 km depth) crustal conditions during pluton emplacement. This is interpreted to reflect loading due to the emplacement of Taconic allochthons during the waning stages of regional metamorphism before emplacement of the plutons. The second study uses thermodynamic heating calculations of pelitic schist to determine the production of norite and emery. Modeling results produce (i) an initial melt that produces a monzonorite composition when mixed with a mafic melt, (ii) a high-T melt that is texturally and compositionally homologous with quartzofeldspathic veins retained in the emery, and (iii) a residual mineral assemblage that, when oxidized, closely resembles the emery assemblage. Finally, focus is given to understanding the relationship between norite and emery and reflection on the mineralogy and structure of the lower crust-mantle boundary. Density calculations of the emery estimate values comparable to mantle densities, implying that rare exposure of UHT assemblages may be due to the fact the material stays at lower crustal (upper mantle?) depths. Therefore, the less-rare norite and other hybrid igneous rock occurrences may be the traces of deep, unexposed, UHT metamorphic assemblages. / Ph. D.

The time dependence of the physical properties of ethylene/1-octene (EO)-copolymers after primary crystallization is investigated by calorimetry, density, and creep measurements. The temporal evolution of the multiple melting of EO-copolymers is monitored by differential scanning calorimetry. The low temperature endotherm displays an evolution similar to that observed for the enthalpy recovery in glasses after physical aging. Using this analogy, a calorimetry-aging rate is defined, which quantifies the change in the low endotherm temperature with time. Similarly a density-aging rate is defined from the evolution of density with time. A non-classical creep behavior is observed for short aging times, consistent with crystallization-induced shrinkage. The change in crystallinity during aging leads to a change in the shape of the relaxation spectrum. Hence, analysis of creep data cannot be carried out using Struik's superposition method. For both short and long aging times, the creep rate exhibits a dependence on copolymer composition similar to those associated with the calorimetry- and the density-aging rates, suggesting a common origin for the evolution of the low endotherm, the creep behavior and the bulk density. The calorimetry, density, and creep data are reexamined based on the following assumptions: First, a single population of small crystals is formed during crystallization at low temperature; Second, these small crystals increase in stability under isothermal conditions, easily melt and recrystallize during heating and serve as efficient thermo-reversible cross-links to increase the conformational constraints in the residual amorphous fraction. These assumptions appear to be consistent with all observations made to date. / Master of Science

The relationship between substituent chemistry and melt behavior for xylan derivatives was investigated by differential scanning calorimetry and parallel-plate dynamic viscometric measurements. Xylan esters exhibit characteristic Tg values which decrease with increasing size of substituent. However, these materials do not flow at temperatures well above Tg. The ether derivative hydroxypropyl xylan was found to flow at substitution levels higher than 0.5 degree of substitution, with melt viscosity decreasing as the degree of substitution increased. The influence of viscosity ratio and composition on the texture of melt-blends of hydroxypropyl cellulose and polystyrene was studied for viscosity ratios of 0.08 to 0.55. Blends were examined by SEM and TEM. It was found that composition was the determining factor in texture, and not viscosity ratio over the range tested. Extrusion problems limited the range of compositions tested to 40% biopolymer or less. Phase inversion was not observed, although inversion was expected for some samples based on predictive models in the literature. / Master of Science

En utilisant des solutions de production issues des technologies de Fabrication Additive (FA), l’industrie s’ouvre de nouvelles possibilités pour la fabrication de pièces à haute valeur ajoutée. Dans le but d’être pleinement exploitables, ces procédés de fabrication doivent permettre la réalisation de pièces dont la qualité est adaptée aux besoins de l’industrie. Ces travaux se concentrent sur deux points ciblés de la maîtrise de la qualité en FA appliquée à la technologie Electron Beam Melting (EBM).Le premier point abordé s’intéresse à l’impact de la position d’une pièce dans l’espace de fabrication d’une machine sur la qualité géométrique de cette pièce. Pour caractériser l’espace de fabrication de la machine Arcam A1, plusieurs séries de pièces sont fabriquées à différentes localisation de l’espace, puis comparées à leur design initial. Les écarts mesurés entre les pièces et leur géométrie souhaitée montrent que la périphérie de l’espace de fabrication est une zone sujette à d’importants défauts géométriques. Ces défauts sont caractérisés et des solutions sont proposées pour en limiter l’impact sur la qualité géométrie des pièces.Le second point traite de la porosité des pièces fabriquées. Lorsque l’apport énergétique du faisceau d’électron n’est pas adéquat pour fondre correctement la poudre, des pores peuvent se former dans le matériau des pièces fabriquées. La géométrie et le matériau des pièces rendent difficiles la détection de ses pores. Une méthode de détection est proposée pour détecter la présence de pores dans une pièce via un contrôle standardisé sur un élément qui copie les conditions de fusion de la pièce. Cette méthode propose deux alternatives de contrôle : un contrôle optique (rapide, abordable mais peu précis) et un contrôle tomographique (plus précis que le précédent mais moins rapide et abordable). Un algorithme de traitement d’image innovant a été développé dans le cadre de cette étude afin de rendre les tomographies du témoin plus fiables. / By using production solutions from Additive Manufacturing (AM) technologies, the industry is opening up new possibilities for manufacturing high added value parts. In order to be fully exploitable, these manufacturing processes must allow the production of parts whose quality is adapted to the needs of the industry. This work focuses on two aiming points of quality control in AM applied to Electron Beam Melting (EBM) technology.The first point deals with the impact of a part position in the manufacturing space of a machine on the geometric quality of this part. To characterize the manufacturing space of the Arcam A1 machine, several series of parts are manufactured at different locations of the space, then compared to their initial design. The differences measured between the parts and their desired geometry show that the periphery of the manufacturing space is a zone subject to important geometrical defects. These defects are characterized and solutions are proposed to limit the impact on the geometrical quality of parts.The second point deals with the porosity of manufactured parts. When the energy supply of the electron beam is not adequate to melt the powder properly, pores can form in the material of the manufactured parts. The geometry and material of the parts make it difficult to detect its pores. A detection method is provided to detect the presence of pores in parts via a standardized control on an item that copies the parts merging conditions. This method offers two control alternatives: an optical control (fast, affordable but not very accurate) and a tomographic control (more accurate than the previous one but slower and costlier). An innovative image processing algorithm is developed as part of this study to make the item tomography scans more reliable.

The focus of this literary study was additive manufacturing (AM) and the purpose was to find general trends for selected materials that have been additively manufactured and compare them to results from other reviews. The raw materials studied were stainless steels 316L, 17-4 PH, 15-5 PH and 420, as well as tool steel H13 and nickel alloys 625, 718 and Hastelloy X.The AM techniques studied were selective laser melting (SLM), electron beam melting (EBM) and binder jetting (BJG).  A total of 69 articles have been studied to fulfill the purpose above. The articles were used to write a summary of the techniques, compare them to each other and to conventional methods. They were also used to create a database to compile information on mechanical properties, microstructure and process parameters. Based on the database mechanical properties for SLM tend to be higher compared to EBM. This however varied somewhat depending on the processed material. Furthermore the yield and tensile strength obtained from the database for SLM seemed to be higher compared to the values in review articles for almost all materials. Unfortunately not enough values were found for BJG to compare it to SLM and EBM.AM seems to produce weaker, equal and superior products compared to conventional methods. However due to the limited nature of the project and the research found no conclusions can be drawn about any trends, how to achieve the different results or how parameters affect the finished product. To be able to say anything with more certainty more research has to be done. Not only in general concerning the AM techniques, but more studying of existing articles is needed. Finally a standardization on how to reference properties and process parameters is necessary. Currently it is very difficult to compare results or draw conclusions due to different designations, units and a lot of missing essential information.

The focus of this literary study was additive manufacturing (AM) and the purpose was to find general trends for selected materials that have been additively manufactured and compare them to results from other reviews. The raw materials studied were stainless steels 316L, 17-4 PH, 15-5 PH and 420, as well as tool steel H13 and nickel alloys 625, 718 and Hastelloy X. The AM techniques studied were selective laser melting (SLM), electron beam melting (EBM) and binder jetting (BJG).  A total of 69 articles have been studied to fulfill the purpose above. The articles were used to write a summary of the techniques, compare them to each other and to conventional methods. They were also used to create a database to compile information on mechanical properties, microstructure and process parameters. Based on the database mechanical properties for SLM tend to be higher compared to EBM. This however varied somewhat depending on the processed material. Furthermore the yield and tensile strength obtained from the database for SLM seemed to be higher compared to the values in review articles for almost all materials. Unfortunately not enough values were found for BJG to compare it to SLM and EBM.AM seems to produce weaker, equal and superior products compared to conventional methods. However due to the limited nature of the project and the research found no conclusions can be drawn about any trends, how to achieve the different results or how parameters affect the finished product. To be able to say anything with more certainty more research has to be done. Not only in general concerning the AM techniques, but more studying of existing articles is needed. Finally a standardization on how to reference properties and process parameters is necessary. Currently it is very difficult to compare results or draw conclusions due to different designations, units and a lot of missing essential information.

Les procédés de fabrication additive ont connus un fort essor dans les dernières décennies et entament aujourd'hui leur phase d'industrialisation pérenne. L'industrie, dans un souci d'améliorer sans cesse le ratio masse/rigidité des systèmes qu'elle produit (notamment l'industrie aéronautique), a pris conscience du potentiel de ces technologies à produire des structures plus complexes que les procédés classiques. Elle cherche aujourd'hui à tirer profit de ce potentiel pour alléger encore plus les pièces produites en utilisant notamment des géométries de type réseaux ou alvéolaires (Lattice en anglais). Les travaux présentés dans ce manuscrit ont pour but de proposer une méthodologie, des modèles et des outils permettant la conception, le dimensionnement et l'optimisation de telles structures en vue de leur fabrication par procédés additifs. Le framework proposé peut être résumé par les huit étapes ci-dessous:- Importation de l'espace de conception, comprenant également les cas de chargement.- Optimisation topologique sur l'espace de conception.- Reconstruction de la géométrie, appelée primitive, qui servira de support à l'insertion du réseau.- Calcul par éléments finis qui peut être réalisé pour s'assurer de la bonne tenue mécanique.- Définition de la topologie du réseau, par l'intermédiaire d'un graphe 3D.- Déformation du réseau et optimisation mécanique du réseau.- Reconstruction des volumes.- Préparation des fichiers de données et impression 3D. / Additive manufacturing processes have been quickly growing those past decades and are now getting to their sustainable industrial. Industry has been caring about the mass to rigidity ratio of the structures it produces (especially in aeronautics), and is now acknowledging the potential of additive processes to produce more complex shapes than classical processes. Industry is now trying to take advantage of this potential by designing highly complex structures like lattices or metal foams. The work that is presented in this document propose a methodology, models and numerical tools allowing the conception, dimensioning and optimization of such structures through additive manufacturing. The proposed framework can be describe through the height following steps:- Importing the design space and the technical requirement (load cases).- Topology optimization of the design space- Geometry reconstruction to create a primitive which will be the lattice insertion area.- Finite elements computation to ensure that the structure meets the requirements.- Lattice topology definition using 3D graphs.- Lattice deformation and optimization.- Creation of the volumes around the lattice.- Printing file creation and 3D printing.

Grâce à la fabrication additive, il est aujourd'hui possible de fabriquer de nouvelles géométries. Les perspectives offertes par les moyens de fabrications conventionnelles et additives sont très différentes. Des propositions de design très contraintes peuvent devenir beaucoup plus libres avec la fabrication additive. Cette liberté qu'elle offre fait émerger une multitude de possibilités. Dans ce manuscrit, nous nous sommes focalisés sur un type particulier de structures (les octetruss) ainsi que sur les moyens de fabrication EBM (Electron Beam Melting) de la société ARCAM. Les travaux présentés dans cette thèse ont été réalisés au sein des laboratoires G-SCOP et SIMAP ainsi qu'en partenariat avec l'entreprise POLY-SHAPE. Ce manuscrit est articulé autour de trois principaux points.Il s'agit tout d'abord de faire émerger des structures treillis lors du processus de conception. Pour cela, deux approches existantes sont détaillées. La première met en œuvre l'optimisation topologique et la seconde s'appuie sur le concept de matériau équivalent. Ensuite deux méthodologies permettent de faire émerger des zones dans lesquelles l'intégration de structures treillis est adaptée. La première consiste à réaliser les différentes zones en s'appuyant sur un champ de contraintes issu d'un calcul Eléments Finis, la seconde se base sur un résultat d'optimisation topologique pour établir les différentes zones. Cette seconde méthodologie est appliquée à un cas d'étude industriel.Ensuite nous étudions comment remplir les différentes zones avec des structures treillis adaptées en nous focalisant tout d'abord sur leur génération. Un accent particulier est porté sur l'intersection des différents barreaux par la mise en place de sphères. Une méthodologie permettant de générer des arrondis est également proposée. Une étude est menée sur l'ensemble des paramètres et informations à considérer pour intégrer une structure treillis à une zone donnée. Cette étude conduit à une proposition de méthodologie qui est appliquée à un cas d'étude industriel.Enfin, les aspects liés à la fabrication sont pris en compte. Pour cela, nous considérons différentes limites du moyen de fabrication EBM pour des structures treillis comme les dimensions maximales réalisables ou les problématiques thermiques. Une étude consistant à prédire la dépoudrabilité des pièces est réalisée. Enfin, des essais mécaniques sont effectués. Nos résultats sont comparés à ceux obtenus dans d'autres travaux. L'impact des arrondis sur le comportement mécanique d'une pièce est discuté. / Thanks to additive manufacturing, it is now possible to manufacture new geometric shapes. The prospects offered by the methods of conventional and additive manufacturing are very different. Highly constrained design proposals can become much freer with additive manufacturing. The freedom it offers brings forward a multitude of possibilities. In this manuscript, we focused on a particular type of structures (the octetruss) as well as the use of EBM (Electron Beam Melting) of ARCAM as a means of manufacturing. The work presented in this thesis was carried out in the laboratories G-SCOP and SIMAP as well as in partnership with the company POLY-SHAPE. This manuscript focuses on three main points.The first of which is the action of emergence of lattice structures during the design process. For this, two existing approaches are detailed. The first uses topological optimization and the second is based on the concept of equivalent material. Following these, there are two methodologies used to identify areas in which the integration of lattice structures is possible and appropriate. The first consists of creating the different zones by relying on a stress field resulting from a finite element calculation, the second establishes the different zones using a topological optimization result. This second methodology is applied to an industrial case study.Secondly, we study how to fill the different areas with appropriate lattice structures by focusing first on their generation. Particular emphasis is placed on the intersection of the various bars by the establishment of spheres. A methodology for generating rounded-shape is also proposed. A study is carried out on all the parameters and information in order to integrate a lattice structure to a given area. This study leads to a proposed methodology that is applied to an industrial case study.Finally, aspects related to manufacturing are taken into account. For this, we consider different limits of the EBM manufacturing and what they mean for lattice structures; such as maximum achievable dimensions or thermal problems. A study to predict powder removal in order to extract the fabricated structure is performed. Mechanical tests are carried out. Our results are compared to those obtained in other works. The impact of curve on the mechanical behavior of a product is discussed.