Apprenant de la nature, les architectures spécifiques de certains organismes vivants sont devenues l'une des idées dominantes dans le développement de nouvelles générations de matériaux synthétiques. Dans cette optique, la structure lamellaire de la nacre peut servir de modèle pour la fabrication de nouveaux matériaux composites à matrices métalliques. Un nouveau procédé de métallurgie des poudres, appelée métallurgie des poudres « plaquettes » (FPM), a ainsi été développée pour fabriquer des matériaux composites à matrice métallique à structure lamellaire.L’objectif de ce travail de thèse est l'utilisation du procédé FPM (en utilisant le broyage mécanique (BM) et le frittage SPS), pour la fabrication de matériaux architecturés lamellaires et bioinspirés de structure nacre. Nous avons montré la possibilité de fabriquer, à partir de poudre plaquettes, des matériaux lamellaires anisotropes monolithiques à base de titane et d’alliages de titane ainsi que des matériaux composites Ti/C. Nous avons également montré les avantages de l'architecture multicouches sur l'amélioration des propriétés mécaniques (dureté) du Ti et de TA6V avec une anisotropie de la dureté entre les sections transversale et longitudinale. L’augmentation de la dureté de ces matériaux lamellaires, par rapport aux matériaux non-lamellaire, est liée principalement à l'épaisseur des "plaquettes" qui est contrôlée par le temps de BM, ainsi que par l’effet de la microstructure affinée et de l’écrouissage du matériau lamellaire.Nous avons également montré la possibilité de fabriquer des matériaux composites lamellaires in-situ Ti/TiC par BM (en présence d'acide stéarique) et frittage SPS, avec la possibilité de contrôler la teneur en TiC en jouant sur les conditions de BM (temps BM et taux d’acide stéarique). Ce matériau composite permet une amélioration de la dureté et du module de Young attribuée à la phase de TiC formée. / Learning from nature, biological design has become one of the prevailing ideas in developing new generations of synthetic materials. In the strengthening and toughening exploration of composite materials, nacre lamellar structure may serves as a model system of tremendous interest. A novel powder metallurgy (PM) strategy, called flake PM, was developed to fabricate bulk metal matrix composite materials with laminated structure.The aims of this thesis is the use of flakes PM (using ball milling and SPS sintering), for the fabrication of biomimetic titanium and titanium alloys nacre’s laminated structures and of titanium/carbon composite materials. This process showed the possibility of the fabrication of laminar material with anisotropic microstructure. We proved the advantages of the layer’s architecture on the improvement of Ti and TA6V mechanical properties (hardness) with hardness anisotropy between the cross section and the longitudinal one. The hardness of this material is related to the thickness of the "flakes" which is controlled by the time of BM. This strengthening was also attributed to the flake thickness, the refined microstructure and the hardening of the lamellar material.We showed also the possibility of fabrication of in-situ Ti/TiC laminated composite materials using BM (in the presence of stearic acid) and SPS sintering, with the possibility of the control of TiC content by controlling the BM conditions (BM time and stearic acid amount). This composite material exhibit improvement of the hardness and Young’s modulus, attributed to the TiC phase formed.

Vitellogenesis in two caryophyllidean cestodes Caryophyllaeus laticeps and Khawia sinensis, parasitizing cyprinid fishes, were examined using light(LM)and transmission electron microscopy(TEM)and cytochemical staining for glycogen. Mature vitelline folicles consist of vitelline cells at various stages of development and an interstitial tissue. Maturing and mature vitellocytes contain vitelline material in the form of single small shell globules, which fuse and give rise to the large shell globule clusters.Glycogen was present in the cytoplasm and in the nucleus of the mature vitellocytes. Small lipid droplets were found in the cytoplasm of C. laticeps. "Lamellar granules" were observed in the cytoplasm of the mature vitellocytes in K. sinensis.

Atualmente, tem se dado grande importância à criação de novos sistemas de liberação de princípios ativos. Na área cosmética, os sistemas em destaque são nanoemulsões, emulsões múltiplas e emulsões contendo cristais líquidos/fase gel lamelar. Nas emulsões múltiplas coexistem emulsões dos tipos O/A e A/O. Elas possuem inúmeras vantagens sobre outros sistemas de liberação, como por exemplo, a possibilidade de veicular dois ativos incompatíveis em compartimentos diferentes e controlar o perfil de liberação dos mesmos. Além disso, possuem biocompatibilidade, completa biodegradabilidade e podem ser usados diferentes óleos e tensoativos. Outra tendência recente em cosmetologia é o emprego de matérias-primas vegetais associadas a sistemas de liberação de princípios ativos, para formulação de novos produtos com apelo comercial e sustentável. O objetivo deste trabalho foi desenvolver um novo sistema de emulsão múltipla, por etapa única, que tivesse estabilidade características diferenciadas. Para tanto, elegeu-se dois óleos vegetais: girassol e gergelim, que foram usados separadamente no desenvolvimento dessas emulsões. O método de emulsificação utilizado foi o método de inversão de fases (EPI). Foi determinado o EHL crítico para cada um dos óleos, 6,5 para o óleo de girassol e 5,0 para o óleo de gergelim. Os pares de tensoativos escolhidos para o estudo foram Steareth 2 - Steareth 20 para óleo de girassol e Span® 60 - R400 para óleo de gergelim. Foram construídos dois diagramas pseudoternários, um para cada sistema, com o objetivo de definir variáveis relevantes à composição (fração aquosa, fração oleosa, porcentagem de tensoativo). Foram selecionadas as melhores emulsões para prosseguimento dos estudos de estabilidade, avaliada por meio dos seguintes testes físico-químicos: medições de pH, condutividade elétrica, granulometria e medidas reológicas. O método de emulsificação em etapa única por inversão de fases se mostrou eficiente na produção de emulsões múltiplas estáveis. Foi desenvolvida uma emulsão múltipla com características diferenciadas a partir do óleo de girassol: emulsão múltipla contendo fase gel-lamelar, um sistema ainda não descrito na literatura. As características das emulsões múltiplas descritas nesse trabalho, a saber: o uso de óleos vegetais como os óleos de girassol e gergelim; baixas concentrações de tensoativos; multiplicidade dos glóbulos e fase gel lamelar no mesmo sistema; são características desejáveis para a indústria cosmética, o que as tornam potenciais sistemas de liberação de ativos. / Currently, it has been given great importance to the creation of new delivery systems for active ingredients. In the cosmetic area, the highlighted systems are nanoemulsions, multiple emulsions and liquid crystal/lamellar gel phase emulsions. In multiple emulsions coexist O/W and W/O types of emulsions. They have several advantages over other delivery systems, such as the possibility of carry out two incompatible active ingredients in different compartments and the control of the release of the same. Moreover, they have biocompatibility, biodegradability and different oils and surfactants can be used. Another recent trend in cosmetology is the use of vegetable raw materials associated with the delivery systems for active ingredients, to formulate new products with commercial and sustainable appeal. The objective of this study was to develop a new system of multiple emulsion, in one step emulsification, which have stability and distinctive features. It was selected two vegetable oils: sunflower and sesame, which were used separately in the development of the multiple emulsions. The method of emulsification used was emulsion phase inversion (EPI). The critical HLB of oils was, 6.5 for sunflower oil and 5.0 for sesame oil, respectively. The pairs of surfactants chosen for the study were Steareth 2 - Steareth 20 for sunflower oil and Span® 60 - R400 for sesame oil. We constructed two pseudo-ternary diagrams, one for each system, in order to define variables relevant to the composition (water and oil fraction, percentage of surfactant). We selected the best emulsions for further investigation. Stability of the emulsions was evaluated by the following physico-chemical tests: measurements of pH, electrical conductivity, particle size and rheological measurements. The method of one-step emulsification was efficient in producing stable multiple emulsions. A multiple emulsion from sunflower oil was developed with distinctive features: gel-lamellar phase multiple emulsion, a system not described yet. The characteristics of multiple emulsions described in this work, to know: use of vegetable oils, as sunflower and sesame oils; low concentrations of surfactants; multiplicity of droplets and lamellar gel phase at same system; they are desirable characteristics for the cosmetic industry, and they make these multiple emulsion potential delivery systems.

Automotive industry products portfolio includes a wide variety of complex‐shaped cast iron products, such as truck engine components, that need to withstand a constant trend of higher demands, especially urged by stricter environmental regulations on emissions. Combined with this continued demand on properties improvement, cast iron industry faces a process problem related to the lack of understanding of solidification and mechanisms behind defect formation. Casting products are highly affected by the product design and the manufacturing method itself, which governs the final microstructure and hence the final mechanical properties. Wall thickness of the moulding material strongly influences the solidification time, varying the microstructural coarseness, resulting in a component with different properties depending on the local shape of the casting. The main objective of this work is the characterization of the primary austenite microstructure and its coarsening process, which has been poorly documented in cast iron literature, to allow the prediction and control of these microstructural features present in the casting. The microstructural evolution of the primary austenite in hypoeutectic lamellar graphite iron (LGI) is studied under isothermal coarsening conditions. The dendritic microstructure suffered major morphological changes that included dendrite fragmentation, globularization, and coalescence. Empirical relations based on morphological parameters are introduced to predict the microstructural evolution of primary austenite. A novel technique for colour‐etching and semi‐automatic image analysis for the characterization of quenched dendritic microstructures in cast iron is presented. A new experimental technique for production of graphitic iron with varying nodularity is presented as a solution to control the production of compacted (CGI) and spheroidal graphite iron (SGI) under laboratory conditions. The nodularity evolution is controlled as a function of the holding time and the residual Mg, allowing the study of the primary solidification and primary microstructures of hypoeutectic CGI and SGI in future investigations.

Les lubrifiants à base aqueuse sont très largement utilisés dans les procédés de mise en forme des métaux comme le tréfilage, car ils combinent d’excellentes capacités calorifiques à de bonnes propriétés tribologiques. Pour répondre à des exigences d’augmentation de la productivité, la compréhension des mécanismes de lubrification est nécessaire. L’objectif de ces travaux est d’établir le lien entre l’organisation des molécules en solution dans le lubrifiant et son pouvoir lubrifiant. La démarche expérimentale consiste à déterminer les propriétés structurales et tribologiques d’un système modèle aqueux, composé d’acides gras et d’éthylène diamine, principaux ingrédients des lubrifiants. Le diagramme de phases du système modèle est établi en s’appuyant sur des techniques de microscopie optique de polarisation, diffusion des rayons X aux petits angles (DXPA) et cryofracture. Pour un rapport molaire entre la diamine et les acides gras supérieur à 1, une succession de phases lamellaire, hexagonale et micellaires, biréfringente sous écoulement et isotrope, est observée avec la dilution. Une attention particulière est accordée à la phase lamellaire qui présente des défauts à l’approche de la transition vers la phase hexagonale. Les analyses réalisées en DXPA, cryofracture et RMN relient leur existence à une modulation de l’épaisseur de la bicouche et une augmentation de la courbure liées au couplage entre les acides gras et les contre-ions amines. Les propriétés lubrifiantes de l’ensemble de ces phases sont également comparées à l’aide d’un tribomètre qui réalise un contact entre un disque et une bille sous une cinématique de contact contrôlée, en régime de lubrification élastohydrodynamique. En plus des mesures de frottement, l’observation simultanée du contact permet de suivre la formation du film lubrifiant entre les surfaces et son évolution. L’influence de l’organisation supramoléculaire du lubrifiant sur son comportement est mise en évidence : les échantillons présentant une organisation lamellaire fournissent les meilleurs résultats en termes de réduction du frottement. L’organisation en bicouches de la phase lamellaire au sein du contact et ses propriétés piézovisqueuses peuvent expliquer sa portance accrue et sa prédisposition naturelle à la réduction du frottement. / Water based lubricants are widely used in metal forming processes due to their good cooling and lubrication capabilities. The understanding of the lubrication mechanisms is necessary to improve the current lubricant efficiency. The goal of this work is to correlate the structural properties of the lubricant to its lubricating behaviour. As mixtures of ethylene diamine and fatty acids in water are some of the main ingredients of such lubricants, their phase behaviour and tribological properties are investigated for different compositions. The phase diagram of the model system is established by using optical microscopy of polarisation, small angle X-rays scattering (SAXS) and freeze-fracture transmission electron microscopy (FF-TEM). For a molar ratio between diamine and fatty acids upper to 1, a succession of lamellar, hexagonal and micellar phases is observed with the dilution. A particular attention is turned to the lamellar phase which presents defects close the transition towards the hexagonal phase. According to SAXS, nuclear magnetic resonance and FF-TEM analyses, we propose that their existence is due to a modulation of the bilayer thickness and an increase of the curvature resulted from the evolution of the coupling between the fatty acids polar heads and the amine counter-ions. The lubricating ability of these phases is then investigated experimentally using an EHL tribometre that simultaneously enables contact visualisation, film thickness and friction measurements in controlled kinematic conditions. The influence of the lubricant structure on its tribological behaviour is revealing: the lowest friction coefficients are obtained with lamellar samples. The organisation in bilayers of the lamellar phase within the contact and its piezoviscous properties can explain its greater load-bearing capacity and its natural predisposition to the reduction of the friction.

Cette thèse porte sur la relation entre le procédé de préparation et la structure des nanocomposites polypropylène/argile. Les échantillons ont été préparés au mélangeur interne dans un premier temps. Des observations au microscope électronique à balayage, complétées par des analyses en diffraction des rayons X ainsi que des mesures rhéologiques ont permis de caractériser l’état de dispersion de l’argile à différentes échelles au sein du matériau. Nous avons comparé trois argiles organophiles et montré que la compatibilité chimique entre l’argile et la matrice est un facteur primordial afin d’obtenir une bonne dispersion : la Cloisite 20 et la Dellite 67G montrent de bons états de dispersion à toutes les échelles au contraire de la Cloisite 30B. Nous avons ensuite mis en évidence l’influence de la vitesse de rotation ainsi que du temps de mélange sur l’état de dispersion de l’argile. Le seuil de percolation de l’argile dans le polypropylène a été déterminé. Le lien entre état de dispersion et cristallinité du polypropylène a également été étudié.Les échantillons ont ensuite été préparés par extrusion bivis. L’influence de la vitesse de rotation sur l’état de dispersion de l’argile a été mise en évidence, tout autant que la dégradation de la matrice aux plus fortes vitesses. L’évolution de l’état de dispersion le long de la vis a montré que si l’intercalation était rapidement atteinte sur la vis, l’exfoliation progressait linéairement avant de saturer sur les dernières zones. L’utilisation d’une température de régulation plus faible ou d’une matrice plus visqueuse n’ont pas permis d’améliorer l’état de dispersion de l’argile ni d’éviter la dégradation de la matrice. Enfin, l’utilisation du logiciel Ludovic© a permis de mieux appréhender les phénomènes thermomécaniques mis en jeu lors de l’extrusion, mais également d’optimiser le procédé. / This PhD focuses on the relationship between the preparation process and the structure of polypropylene/clay nanocomposites. First, the samples were prepared via an internal mixer. Scanning electron microscopy observations, completed by X-ray diffraction analysis and rheology measurements enabled us to characterize the clay dispersion state in the nanocomposite at different scales. Three organoclays were compared. It was shown that the chemical compatibility between the clay and the matrix was essential to ensure a good dispersion: Cloisite 20 and Dellite 67G showed good dispersion states at all scales, whereas Cloisite 30B did not. The influence of rotor speed and mixing time on the clay dispersion state was shown. The percolation threshold of the clay was determined. The link between dispersion state and crystallinity was also studied.The samples were then prepared via a twin-screw extruder. The influence of screw speed on the clay dispersion state was demonstrated, as well as the matrix degradation at high screw speed. The evolution of the dispersion state along the screw profile showed that intercalation was reached early in the screw profile, whereas exfoliation evolved linearly until the last mixing elements. A lower barrel temperature, as well as a more viscous matrix did not improve the clay dispersion state, and did not prevent the matrix degradation. Finally, the Ludovic© software allowed us to apprehend the thermomechanical phenomena involved during extrusion, but also to optimize the process.

The main subject of the diploma thesis is a new construction of the hotel with sporting facility in Kuřim. The Thesis is done in a form of a project documentation with all requests by the law and regulations included. The project is Composed of two buildings, a hotel and the sporting hall. The building is Located in slope in direction to south direction. The hotel building have four Storeys. The whole disposition solution of both buildings is connected. In a first floor is located the hotel restaurant, staff background, wellness and fitness Secon and third floor is supposed to be Used Mainly for accomodating of Sportsmans, and the last fourth floor is for holding meetings and conferences. The main Supporting structure is done with as monolitic frame construction of beams, columns and continuous slabs. All roofs are done as mono-layer roofs. First floor of the sporting hall is used by people during the sporting activity. This area is composed of changing rooms with a social background and other spaces for the proper function of the hall. The main Supporting construction of the hall is designed as glued lamellar beams supported by columns.

Chiral magnets such as MnSi, FeGe or Cu2OSeO3 exhibit a non-centrosymmetric lattice structure which lacks inversion symmetry. The resulting Dzyaloshinskii-Moriya interaction originating from weak spin-orbit coupling stabilizes smooth modulated magnetic textures, namely helices and skyrmions. In this thesis, we study the properties of helimagnets which are systems with a magnetic helix as ground state. First, we examine the consequences of the helical texture for spin wave excitations, so-called helimagnons. We investigate magnon-focusing effects, i.e. magnon flow in very specific directions, which result from flat bands occurring in the helimagnon band structure when the momentum component perpendicular to the helix axis is large. We show that the softness of the Goldstone mode leads to a large dissipation even at very small frequencies cut off only by magnetocrystalline anisotropies or by a magnetic field. Finally, we discuss that dipolar interactions induce non-reciprocal behavior of the spectrum at finite fields and momenta, i.e. the spectrum is not symmetric under reversing the momentum anymore. We calculate the Brillouin light scattering cross section and compare it to experimental results obtained by N. Ogawa [1]. Then, we consider reorientation processes of the helix axis due to an applied magnetic field. We compare the results to magnetic force microscopy measurements in Cu2OSeO3 performed by P. Milde et al. [2]. Afterwards, we point out that the skyrmion lattice orientation has singular points, i.e. points where the orientation is not determined, as a function of the magnetic field direction which is a consequence of the Poincaré-Hopf theorem. Afterwards, we turn to excitations in the form of the basic defects in helimagnets: disclinations and dislocations. Due to the lamellar nature of the helimagnetic texture, analogies to liquid crystals can often be used. We present an analytic parameterization of dislocations transferred from smectic liquid crystals and illustrate that dislocations carry a topological skyrmion charge. We examine dislocation motion in the presence of weak pinning due to random impurities. We derive a Thiele-Langevin equation for the dislocation position which effectively describes one dimensional motion. When reducing the system to two dimensions, this reveals ultra slow anomalous Sinai diffusion which may explain the very long time scales observed in several experiments [3,4]. Eventually, we present our work on domain walls in helimagnets. In magnetic force microscopy experiments performed by P. Schoenherr [5], we have identified three domain wall types. At small angles between the two domains, curvature walls appear. At intermediate angles, one can observe zig-zag disclination walls and at large angles, dislocation walls occur. We present analytical descriptions for curvature and dislocation walls, which we compare to micromagnetic simulation results obtained by J. Masell [5], and comment on the non-trivial topology of helimagnetic domain walls. [1] N. Ogawa, L. Köhler, M. Garst, S. Toyoda, S. Seki, and Y. Tokura, In preparation (2019). [2] P. Milde, E. Neuber, P. Ritzinger, L. Köhler, M. Garst, A. Bauer, C. Pfleiderer, H. Berger, and L. M. Eng, In preparation (2019). [3] A. Dussaux, P. Schoenherr, K. Koumpouras, J. Chico, K. Chang, L. Lorenzelli, N. Kanazawa, Y. Tokura, M. Garst, A. Bergman, C. L. Degen, and D. Meier, Nature Communications 7, 12430 (2016). [4] A. Bauer, A. Chacon, M. Wagner, M. Halder, R. Georgii, A. Rosch, C. Pfleiderer, and M. Garst, Physical Review B 95, 024429 (2017). [5] P. Schoenherr, J. Müller, L. Köhler, A. Rosch, N. Kanazawa, Y. Tokura, M. Garst, and D. Meier, Nature Physics 14, 465 (2018).:Introduction 1. Introduction to chiral magnets 1.1. Helimagnets 1.1.1. Magnetic phase diagram of chiral magnets 1.2. Skyrmions 1.2.1. Topology 1.2.2. Magnetic skyrmions 1.2.3. Skyrmion motion 1.2.4. Emergent electrodynamics 1.3. Model for chiral magnets 2. Spin waves in helimagnets 2.1. Linear spin wave theory for helimagnons 2.1.1. Fluctuations in the harmonic approximation 2.1.2. Spectrum at small momenta and fields 2.1.3. Frequency broadening from Gilbert damping 2.2. Magnon-focusing effects 2.3. Enhanced local dissipation 2.3.1. Global static susceptibility in the limit k, k' → 0 2.3.2. Local damping 2.4. Non-reciprocity 2.4.1. Non-reciprocity of the spectrum 2.4.2. Brillouin light scattering cross section 3. Orientation of magnetic order 3.1. Helix reorientation transition in MnSi 3.1.1. Effective Landau potential for the helix pitch 3.1.2. Experimental results 3.2. Helix reorientation in Cu2OSeO3 3.3. Skyrmion lattice orientation 4. Disclinations and dislocations 4.1. Liquid crystals 4.1.1. Types of liquid crystals 4.1.2. Energetics of liquid crystals 4.2. Disclinations 4.2.1. Elasticity theory for disclinations 4.3. Dislocations 4.3.1. Volterra process and Burgers vector 4.3.2. Elasticity theory for dislocations 4.3.3. Mermin-Ho relation in helimagnets 4.3.4. Topological skyrmion charge 5. Dislocation motion 5.1. Thiele approach for one helimagnetic dislocation 5.1.1. Motion in the presence of pinning 5.1.2. Corrections from elastic deformations 5.2. Dislocation diffusion 5.2.1. Sinai diffusion and toy model simulations 5.2.2. Susceptibility with Sinai diffusion 5.2.3. Dislocation string 6. Domain walls 6.1. Experimental and numerical methods 6.2. Domain wall types in helimagnets 6.3. Energetics of helimagnetic domain walls 6.3.1. Curvature wall 6.3.2. Dislocation wall 6.4. Topological domain wall structures 7. Discussion and outlook Appendix A. Details on helimagnons B. Formalism of linear-spin wave theory in helimagnets C. Deviations from the helix Bibliography List of Figures Index Danksagung

Narrow molecular weight fractions of Poly(ε-caprolactone) were successfully obtained using the successive precipitation fractionation technique with toluene/n-heptane as a solvent/nonsolvent pair. Calorimetric studies of the melting behavior of fractions that were crystallized either isothermally or under constant cooling rate conditions suggested that the isothermal crystallization of the samples should be used for a proper evaluation of the molecular weight dependence of the observed melting temperature and degree of crystallinity in PCL. The molecular weight and temperature dependence of the spherulitic growth rate of fractions was studied in the context of the Lauritzen-Hoffman two-phase model and the Strobl three-phase model of polymer crystallization. The zero-growth rate temperatures, determined from spherulitic growth rates using four different methods, are consistent with each other and increase with chain length. The concomitant increase in the apparent secondary nucleation constant was attributed to two factors. First, for longer chains there is an increase in the probability that crystalline stems belong to loose chain-folds, hence, an increase in fold surface free energy. It is speculated that the increase in loose folding and resulting decrease in crystallinity with increasing chain length are associated with the ester group registration requirement in PCL crystals. The second contribution to the apparent nucleation constant arises from chain friction associated with segmental transport across the melt/crystal interface. These factors were responsible for the much stronger chain length dependence of spherulitic growth rates at fixed undercooling observed here with PCL than previously reported for PE and PEO. In the case of PCL, the scaling exponent associated with the chain length dependence of spherulitic growth rates exceeds the upper theoretical bound of 2 predicted from the Brochard-DeGennes chain pullout model. Observation that zero-growth and equilibrium melting temperature values are identical with each other within the uncertainty of their determinations casts serious doubt on the validity of Strobl three-phase model. A novel method is proposed to determine the Porod constant necessary to extrapolate the small angle X-ray scattering intensity data to large scattering vectors. The one-dimensional correlation function determined using this Porod constant yielded the values of lamellar crystal thickness, which were similar to these estimated using the Hosemann-Bagchi Paracrystalline Lattice model. The temperature dependence of the lamellar crystal thickness was consistent with both LH and the Strobl model of polymer crystallization. However, in contrast to the predictions of Strobl’s model, the value of the mesomorph-to-crystal equilibrium transition temperature was very close to the zero-growth temperature. Moreover, the lateral block sizes (obtained using wide angle X-ray diffraction) and the lamellar thicknesses were not found to be controlled by the mesomorph-to-crystal equilibrium transition temperature. Hence, we concluded that the crystallization of PCL is not mediated by a mesophase. Metallocene-catalyzed linear low-density (m-LLDPE with 3.4 mol% 1-octene) and conventional low-density (LDPE) polyethylene blends of different compositions were investigated for their melt-state miscibility and concurrent crystallization tendency. Differential scanning calorimetric studies and morphological studies using atomic force microscopy confirm that these blends are miscible in the melt-state for all compositions. LDPE chains are found to crystallize concurrently with m-LLDPE chains during cooling in the m-LLDPE crystallization temperature range. While the extent of concurrent crystallization was found to be optimal in blends with highest m-LLDPE content studied, strong evidence was uncovered for the existence of a saturation effect in the concurrent crystallization behavior. This observation leads us to suggest that co-crystallization, rather than mere concurrent crystallization, of LDPE with m-LLDPE can indeed take place. Matching of the respective sequence length distributions in LDPE and m-LLDPE is suggested to control the extent of co-crystallization. / Ph. D.

The theory of the lamellar eutectoid reaction by volume diffusion has been extended to account for solute segregation within the product phases and the effect of dilute third element additions. It has been demonstrated for symmetric binary systems that the segregation can account for 10% or more of the free energy stored in the product phases and can lead correspondingly to a predicted lamellar spacings appreciably greater than those obtained when segregation is neglected. This segregation is relatively high in the systems Cu-In, Cu-Be and Ag-Cd and may account for the fact that a secondary coarse-grained pearlitic reaction follows the initial fine grained one in these systems. The binary theory has been-used to analyse the available data for the eutectoid reaction in the Cu-Al and Fe-C systems and satisfactory agreement is obtained. The theory for ternary systems, while complete in principle, proves to be. intractable in all but the simplest version of the solution thermodynamics. It is concluded that the effect of the third element on the binary eutectoid reaction is mainly through its effect on the phase diagram, the ternary cross effects in the diffusion matrix tending to cancel out. Any additional element which lowers the eutectoid temperature will retard the reaction. / Thesis / Doctor of Philosophy (PhD)