La popularité des schémas d'homogénéisation classiques, basés sur la solution d'Eshelby du problème de l'inhomogénéité, tient à leur robustesse (des contrastes infinis entre les raideurs des différentes phases sont permis) et leur adaptabilité (les problèmes linéaires aussi bien que non-linéaires peuvent être abordés), la complexité des calculs mis en jeu restant limitée. Le fait qu'ils ne prennent en compte de façon quantitative qu'une quantité restreinte d'informations morphologiques constitue leur principale faiblesse. Ainsi, des problèmes tels que l'influence de la distribution de taille des pores ou l'orientation locale d'inclusions anisotropes leur sont inaccessibles. A l'heure actuelle, seuls de longs calculs complets (par éléments finis/de frontière) permettent d'aborder ces questions. L'objet de ce travail est de mettre au point de nouvelles méthodes d'homogénéisation, de mise en oe uvre plus légère que les éléments finis/de frontière, tout en rendant compte de plus de détails de la microstructure que les techniques basées sur la solution d'Eshelby. Le principe variationnel de Hashin et Shtrikman fournit le cadre mathématique rigoureux dans lequel sont développées deux méthodes. La méthode des inclusions polarisées, tout d'abord, dont le but est le calcul de milieux hétérogènes constitués d'inclusions, plongées dans une matrice homogène. Pour un calcul complet d'une microstructure donnée, il est connu que les méthodes numériques d'homogénéisation par transformée de Fourier rapide (FFT) sont de sérieux compétiteurs des méthodes d'éléments finis/de frontière. Le principe de Hashin et Shtrikman permet de jeter un éclairage nouveau sur ces techniques, et un schéma numérique original d'homogénéisation par FFT est proposé dans un second temps ; il s'avère plus rapide et plus robuste que les schémas existants. L'industrie du ciment pourrait certainement tirer parti de tels schémas d'homogénéisation avancés, puisqu'il est connu que les propriétés macroscopiques des pâtes de ciment dépendent fortement des détails les plus fins (à l'échelle sub-micronique) du réseau poreux (dans la phase CSH{}). Une partie de ce travail est consacrée à la caractérisation de ce réseau à l'aide de deux techniques expérimentales : la diffusion des rayons X aux petits angles, et la microscopie X. L'accent a été placé sur l'interprétation emph{quantitative} de ces expériences, en vue d'améliorer les prédictions des estimations des propriétés mécaniques macroscopiques. Une connexion est établie entre ces deux approches. Cette tentative, encore perfectible, montre que les modèles classiques du CSH{} ne peuvent rendre compte de ces données expérimentales / Classical homogenization schemes, based on the solution to Eshelby's inhomogeneity problem, draw their popularity from the fact that they are both robust (even infinite contrast of the mechanical phases is allowed) and versatile (linear- as well as non-linear mechanical problems can be addressed), while the computations involved are very limited. Their flaw lies in the fact that they incorporate very little morphological information: problems such as the influence of the pore-size distribution, or the local orientation of anisotropic inclusions is out of their reach. Presently, only lengthy full-field calculations (FEM, BEM) can address such issues. The aim of this work is to devise new homogenization techniques, which are not as computationally involved as FEM or BEM calculations, while capturing more details of the microstructure than Eshelby-based techniques. Two methods are developed within the framework of the variational principle of Hashin and Shtrikman, which provides sound mathematical ground. The polarized inclusion method, on the one hand, aims to address composites with inclusions embedded in a homogeneous matrix. On the other hand, FFT-based homogenization techniques are known to alleviate the burden of a full-field calculation carried out with FEM or BEM. With the help of the Hashin and Shtrikman principle, new light is shed on these techniques, and a new, faster and more robust, FFT-based scheme is proposed. The cement industry would certainly benefit from such advanced homogenization schemes, since the macroscopic properties of cement pastes are known to heavily rely on the finest details (at sub-micron length-scales) of the porous network (within the CSH{} phase). Part of this work is devoted to the characterization of this network using two experimental techniques, namely small-angle X-ray scattering and tomography with soft X-ray microscopy. Attempts are made at quantifying the microstructure of CSH{}, in order to improve the estimates of its mechanical properties. A link between these two approaches is established. This attempt, perfectible, shows that popular models for CSH{} cannot account for these experimental data

L’évolution des structures poreuses du graphite et de la vermiculite expansés a été étudiée insitu sous pression uniaxiale. Les propriétés d'un matériau résultant des propriétés intrinsèques à lamatrice et de celles dues à la porosité, les études faites dans ce travail ont porté sur deux échellesdifférentes. Les évolutions structurales de la structure cristalline du graphite et de la vermiculite ontd'abord été étudiées à haute pression en cellule à enclumes de diamant. Cette partie du travail a permisd'établir les équations d'état de la vermiculite et de contribuer, de manière significative, à lacaractérisation de la phase haute pression du graphite: une nouvelle phase, le Carbone Z, a étéproposée après l’analyse des données de la spectroscopie Raman couplée aux simulations. Desdéveloppements techniques ont été particulièrement réalisés pour permettre d’étudier in situl'évolution de la porosité sous pression par diffusion aux petits angles sous pression. L’application dumodèle fractale à l’analyse des données a permis de suivre l’évolution de la dimension fractale et de lasurface spécifique apparente. Les échantillons étudiés sont des formes comprimées de graphite et devermiculite expansés dans lesquelles les plans basaux des cristallites ont une orientation préférentielle.Sous pression uniaxiale, la structure poreuse du graphite expansé comprimé évolue à travers uneffondrement irréversible des pores ou un cisaillement de la matrice suivant l'orientation de la pressionappliquée par rapport à l'orientation préférentielle des plans basaux des cristallites. Des expériencescomplémentaires de mesures électriques et de mesures de la porosité par intrusion de mercure ontpermis de confirmer ces modèles proposés. Dans la vermiculite expansée comprimée, les fissuresapparaissent, de manière générale, sous l’effet de la pression uniaxiale. / The porous structure of expanded graphite and expanded vermiculite has been studied insitu under uniaxial stress. The properties of a porous material being related to the matrix and to theporosity, the in situ evolution under of the crystalline structure (of the matrix) under high pressurehave been first investigated using diamond anvil cell. The equation of state of expanded vermiculitehas been established. This first part of this work allowed giving a particular insight to the study of theunsolved high pressure phase of graphite. Combining Raman scattering data and calculations, a newstructure, called Z-Carbon, has been proposed. Thanks to the specific technical developments of thiswork, the porosities of expanded graphite and expanded vermiculite based systems have been studiedin situ under uniaxial stress. The used of fractal model in data analysis allowed following the evolutionof the fractal dimension and of the apparent specific surface The studied samples were made ofcompressed forms of expanded graphite and expanded vermiculite in which the basal plane of thecrystallites have a preferential orientation. The uniaxial stress was taken perpendicular and parallel tothis preferential direction. The porous structure of the expanded graphite sample was found to undergoan irreversible collapse of the pores or a cracks and creation and propagation. Additional electrical andporosity measurements supported the proposed models. In the expanded vermiculite based systems,the crack apparition was observed under uniaxial stress.

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This thesis investigates the mechanisms behind natural silk spinning by integrating rheology, spectroscopy and small angle scattering to better understand this process and to guide our efforts towards mimicking Nature’s ways of producing high performance fibres. As a result of natural selection, arthropods such as spiders and moths have evolved the ability to excrete silk proteins in a highly controlled manner. Spun from liquid feedstocks, silk fibres are used ex vivo to build structures with mechanical properties currently unmatched by industrial filaments. As yet, relatively little attention has been directed to the investigation of spinning under biologically relevant conditions. To better understand how and why silk is spun, this thesis bridges the gap between liquid silk flow properties and structure development. To directly connect the two, I have developed and deployed novel experimental platforms that combine infrared spectroscopy and small angle scattering with rheology. This approach has clarified long-standing ambiguities on the structural root of silk’s apparently complex flow properties. Small angle scattering revealed the length scales involved in the flow induced solidification under a range of spinning conditions. Mo reover, infrared spectroscopy offered a unique perspective into silk’s formation process immediately after excretion. In a similar manner to the post-extrusion tuning of the properties of partly solidified spider silk filaments, this thesis has revealed that silkworm silk fibres are far from completely formed once excreted. One might describe the filaments of mulberry silkworm as seeded molten polymers that form its hydrogen bonding network and crystallises slowly on site. Consequently, it enlightens that post-spinning conditions are equally paramount for silkworm silk, giving an explanation for the relatively poorer mechanical properties. The comparison of silks from a range of species, allowed this hypothesis to be extended to wild silkworm silk. My insights into spinning had the fortuitous repercussion of facilitating silk fibre solubilisation leading to the development of better artificial silk feedstocks flowing like native silks. With these findings, I believe we are now in an improved position to conceive artificial fibres with properties rivalling those of Nature.

In the beginning of the twenty-first century, educational and commercial institutions have driven the demand for cheap and efficient data storage. The storage medium known as magnetic recording media has remained the mainstay for most computer systems due to its large storage capacity per dollar. With the recording media's ever-increasing storage density has come reductions in the magnetic grain size per bit. At the recording bit's density threshold, the magnetic grains become more susceptible to thermal activation, which can render the storage medium unusable. An accurate characterisation of the recording layer's sub-granular structure is essential for understanding the magnetic and thermal mechanisms of high-density recording media. Small-Angle Neutron Scattering (SANS) studies have been performed to investigate the magnetic and physical properties of longitudinal and perpendicular recording grains. The SANS studies of longitudinal magnetic recording media have probed the recording layer's magnetic grain size at a sub-nanometer resolution. In conjunction with these studies, SQUID magnetometry was used to characterise the recording grain's bulk magnetism. Measurements showed that the recording grain was composed of a ferromagnetic hard core (Co-enriched) and a weakly magnetic shell (Cr-enriched). These results provided important information on the grain's magnetic anisotropy, which determines the recording media's magnetic stability. The polarised SANS studies were used to characterise the recording layer's physical granular structure. It was shown that the physical grain size was comparable to its magnetic counterpart. These physical measurements provided insight into the recording grain's chemical composition. The magnetic properties of perpendicular magnetic recording media were studied using SANS and VSM measurements. The neutron scattering studies revealed that the recording grain was composed of a hard ferromagnetic centre enriched with cobalt. The VSM studies showed that the magnetic recording grains exhibited a large perpendicular magnetic anisotropy. These combined studies provided information on the recording grain's ferromagnetic composition and magnetic stability. The polarised SANS measurements showed the physical grain size to be slightly smaller than its magnetic counterpart. This size difference was attributed to the non-magnetic grain boundary composed of SiO2. The boundary thickness determined the degree of inter-granular exchange coupling. Further polarised studies investigated the recording layers switching behaviour, which revealed more information on the grain's magnetic stability.

Die geordneten mesoporösen Silikamaterialien SBA-15 und MCM-41 zeichnen sich durch lange zylindrische Poren aus, die auf einem 2D-hexagonalen Gitter arrangiert sind. Auf Grund dieser Eigenschaften finden sie vielfach Anwendung in der Industrie, bieten jedoch auch die Möglichkeit Sorptionsvorgänge und die dadurch induzierten Verformungen auf der Nanometerebene zu untersuchen. Dazu werden im ersten Teil dieser Arbeit Kleinwinkelröntgenstreuungsdaten mit Hilfe eines Formfaktormodells angefittet, um die Adsorption von Fluid in den Poren in Abhängigkeit vom Dampfdruck nachvollziehen zu können. Basierend auf diesen Ergebnissen wird ein Gittermodell eingeführt, welches die Vorgänge während der Sorption mit Hilfe heuristischer Füllmechanismen reproduziert und im Abgleich mit experimentellen Daten Auskunft über die Verteilung der Porosität auf Mikro- und Mesoporen in SBA-15 gibt. Weiterhin wird der Einfluss der begrenzten Geometrie auf die Selbstassemblierung von Tensiden in SBA-15 untersucht. Hierzu werden Neutronenstreudaten durch die Kombination eines Formfaktormodells für die Bragg-Streuung und des Teubner-Strey-Modells für die diffuse Streuung modelliert und interpretiert. Der zweite Teil der Arbeit beschäftigt sich mit den elastischen Verformungen der mesoporösen Materialien durch die Fluidsorption. Dazu wird eine Molekulardynamik-Simulation eines Lennard-Jones-Fluids in einer Schlitzpore vorgestellt, um den Ursprung dieser Verformungen auf der mikroskopischen Ebene zu untersuchen. Diese Ergebnisse fließen anschließend in ein makroskopisches Modell eines ganzen Kristalliten des mesoporösen Materials ein, wodurch ein einfaches Multiskalenmodell entsteht. Die makroskopische Ebene wird dabei durch eine Finite-Elemente-Simulation beschrieben, die im Abgleich mit experimentellen Daten weitere Aussagen über die elastischen Eigenschaften des Materials erlaubt. / The ordered mesoporous silica materials SBA-15 and MCM-41 consist of long cylindrical pores arranged on a 2D-hexagonal lattice. Due to these features, they are used for a range of industrial applications but provide also a possibility to study sorption processes and sorption-induced deformations on the nanoscale. In the first part of this work small-angle X-ray scattering data are fitted with a form factor model in order to examine fluid adsorption in the pores. Based on these results a lattice model is introduced which reproduces the sorption process using heuristic filling mechanisms and clarifies how the porosity of SBA-15 is composed out of micro- and mesopores. Furthermore, the influence of the confined geometry on the self-assembly of surfactants in SBA-15 is studied. For this, neutron scattering data are modeled and interpreted by the combination of a form factor model for the Bragg scattering and the Teubner-Strey model for the diffuse scattering. The second part of this work focuses on the elastic deformations caused by fluid sorption in the mesoporous materials. A Molecular Dynamics simulation of a Lennard-Jones fluid in a slit-pore is presented in order to reveal the origin of these deformations on the microscopic scale. These results are subsequently implemented into a macroscopic model of whole crystallite, thereby creating a simple multi-scale model. The macroscopic scale is modeled with a Finite Elements simulation, which by comparison with experimental data delivers further insights into the elastic properties of the material.

Orientador: Flavia Maria Netto / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-09-27T19:42:42Z (GMT). No. of bitstreams: 1 HozUrrejola_LuciadelCarmendela_D.pdf: 2021405 bytes, checksum: 7522596dbd78ae21dcc1d21542fc59d5 (MD5) Previous issue date: 2006 / Resumo: Amostras de ß-lactoglobulina (ß-LG) no estado sólido, com diferentes atividades de água (aw) (0,22; 0,53; 0,74), ou em solução, em concentração de proteína de 3 e 10 mg/mL, foram irradiadas (1-50 kGy) utilizando uma fonte de Cobalto-60. Espalhamento de raios-X a baixos ângulos (SAXS), dicroísmo circular (CD) e fluorescência foram as técnicas utilizadas para estudar as mudanças conformacionais da ß-LG por efeito da irradiação. A proteína irradiada foi também examinada por eletroforese em gel de poliacrilamida (PAGE) e desnaturante (SDS-PAGE) sob condições redutoras e não redutoras, cromatografia de exclusão molecular (SE-HPLC) e ¿SH livre. A ß-LG no estado sólido nas diferentes aw estudadas não foi afetada pela irradiação. As amostras não apresentaram diminuição na digestibilidade sob ação da pepsina e tripsina e não mudaram seu poder ligante de retinol quando irradiadas com doses até 10 kGy. Nas amostras irradiadas em solução, houve modificações estruturais, ao nível de estrutura terciária, enquanto a estrutura secundária parece ter sido preservada, como indicado pela quantificação das estruturas obtidas a partir da deconvolução dos espectros de CD no UV-longínquo. Os dados de SE-HPLC e espalhamento de raios-X mostraram que a irradiação promoveu a formação de oligômeros e agregados, que resultaram ser altamente solúveis, como mostrado pelas medidas de turbidez. Da análise dos dados de SAXS e a construção de modelos pode ser mostrado que os oligômeros eram múltiplos de dímeros de ß-LG, (tetrâmeros e hexâmeros, etc.), linearmente ordenados. Ligações cruzadas intermoleculares entre radicais tirosil teriam participação na agregação e as ligações dissulfeto, pelo contrário, não teriam sido relevantes para a formação dos agregados. O mecanismo de agregação da ß-LG mediante ligações cruzadas de bitirosil, contrário ao que acontece em outros tratamentos físicos, como o térmico ou de alta pressão hidrostática, poderia estar gerando agregados com características e propriedades diferentes. O efeito da irradiação na proteína foi maior nas amostras mais diluídas e com maior dose de radiação, indicação da ocorrência do chamado ¿efeito indireto¿ da irradiação. Considerando que não houve alterações estruturais, nem perda de funcionalidade ou de digestibilidade da ß-LG irradiada no estado sólido até com 10 kGy em diferentes aw, o tratamento com radiação gama poderia ser usado para melhorar a qualidade microbiológica da proteína e aumentar as condições de segurança se for aplicada uma radiação na faixa geralmente utilizada no processamento de alimentos (<10 kGy) / Abstract: ß-lactoglobulin (ß-LG) in solution at different protein concentrations (3 and 10 mg/mL) and in solid state, with different water activity (aw) (0.22; 0.53; 0.74), was irradiated using a Cobalt-60 radiation source at a dose level of 1-50 kGy. Small-angle X-ray scattering (SAXS), Circular Dichroism (CD) and Fluorescence spectroscopy were used to study the conformational changes of ß-LG due the irradiation treatment. The irradiated protein was also examined by polyacrylamide gel electrophoresis (PAGE) and sodium dodecyl sulfate (SDS) PAGE under reducing and nonreducing conditions, size exclusion chromatography (SE-HPLC), and free SH. ß-LG in the solid state, at different aw, was not significantly affected by gamma radiation. The digestibility of these samples under pepsin or trypsin action was not diminished, and the retinol binding property was not changed by irradiation up to 10 kGy. The irradiation of ß-LG in solution promoted structural changes at the tertiary structure level but the secondary structure seemed to be maintained, as indicated by the quantification of structures from the deconvolution of the far-UV CD spectra. The SEHPLC, and X-rays scattering data showed that irradiation of ß-LG solutions promoted oligomers and aggregates formation, which proved to be highly soluble, as shown by turbidity measurements. From the SAXS data analyses and the model building it could be shown that the formed oligomers were linear molecules, built by linear combinations of ß- LG dimers (tetramers, hexamers, etc.). Formation of intermolecular cross-linking between tyrosil radicals are proposed to be at least partially responsible by this occurrence, and the disulphide bonds, in contrast, do not appear to be relevant to the formation of these aggregates. The mechanism of aggregation of ß-LG through bityrosil cross-links, differently from the mechanism occurring in other physical treatments as heating or high pressure, could form aggregates with special and different characteristics. The radiation effect was more significant at low protein concentration and higher irradiation dose, being consistent with the occurrence of the ¿indirect effect¿ when proteins are irradiated in solution. Considering that neither structural changes or loss of functionality and digestibility of ß-LG irradiated in the solid state at different aw, with dose up to 10 kGy, was detected, the gamma radiation treatment could be used for improving the microbiological quality of the protein, enhancing the safety conditions when applying the radiation range generally used in food processing (<10kGy) / Doutorado / Doutor em Engenharia de Alimentos

Polymere Nanopartikel sind ein vielversprechender Ansatz für die Diagnose und Therapie von Krankheiten. Sie ermöglichen den Einsatz von schwerlöslichen oder instabilen Wirkstoffen. Ein weiterer Vorteil ist die Möglichkeit das Targetings, durch gezielte Modifikationen des Nanopartikels wird der Wirkstoff zum Zielort transportiert und kann dort in der gewünschten Form freigesetzt werden; dadurch könnten bei erhöhter Wirksamkeit die Nebenwirkungen von Medikamenten reduziert werden. Ziel dieser Arbeit war die Untersuchung von physikalischen und biochemischen Eigenschaften von Nanopartikeln bestehend aus einem abbaustabilen Polystyren- Kern und einer biologisch abbaubaren Schale aus Polybutylcyanoacrylat. Es werden Methoden beschrieben, um die Größe, Struktur und den Abbau dieser Wirkstoffträger zu untersuchen. Die untersuchten Nanopartikel zeigen RAYLEIGH-Streuung, sowohl Größe als auch Abbau können durch Messung des Absorptionsspektrums bestimmt werden. Weiterhin konnten diese Eigenschaften mit Hilfe von dynamischer und statischer Lichtstreuung sowie Neutronenkleinwinkelstreuung untersucht werden. Bei letzterer Methode konnte gezeigt werden, dass die Schale größtenteils abgebaut werden kann, während der Kern intakt bleibt. In einem weiteren Teil der Arbeit wurde die Überwindung der Blut-Hirn-Schranke durch polymere Nanopartikel untersucht. Dabei wurde der fluoreszierende Thioflavine als Modellwirkstoffe eingesetzt. Das Durchdringen der Blut-Hirn-Schranke konnte nur mit Nanopartikeln erreicht werden, an deren Oberfläche ein Apolipoprotein E-Peptid gekoppelt war. Es konnte gezeigt werden, das die Nanopartikelschale im Gehirn abgebaut wird, der Wirkstoff freigesetzt wird und an Amyloid β, einem Marker der Alzheimer-Krankheit, bindet.