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O método Umedecimento, Compactação e Secagem (UCOS) (1, 2, 3) produz, a partir de gesso e água, um material de elevada resistência mecânica: até 90 MPa na compressão. Este trabalho apresenta o estudo do comportamento mecânico deste material e como a água, a temperatura, as impurezas e a microestrutura influenciam no seu comportamento. Durante o estudo da adesão intercristalina, foi encontrada presença de água confinada e que é responsável por grande parte da resistência mecânica. Para auxiliar o estudo, foi desenvolvido outro método: Empacotamento Direto do Dihidrato (EDD). Nesta metodologia, é produzido um material com a mesma resistência, porém com algumas diferenças no comportamento mecânico diferente. Através da elevada resistência mecânica alcançada pelos métodos UCOS e EDD, as aplicações do gesso podem ser ampliadas desde que o gesso conformado por tais métodos possuam confiabilidade e segurança. Para avaliar as propriedades mecânicas, a confiabilidade e a segurança de tal material, realizou-se o estudo dos mecanismos tenacificadores e da mecânica da fratura. Os mecanismos tenacificadores estudados neste trabalho são: controle da microestrutura (aumento da superfície de ruptura), introdução de fibras poliméricas (distribuição da tensão na ponta da trinca, ramificação da ponta da trinca e contenção da abertura da trinca) e introdução de adesivo polimérico (melhora a adesão entre cristais e distribui melhor a tensão na ponta da trinca). Os resultados mostram que os compósitos de gesso reforçados com fibras poliméricas e/ou adesivo polimérico possuem elevada resistência e comportamentos mecânicos distintos para cada tipo de compósito e método de conformação. Concluímos que, com o conhecimento adquirido, é possível intervir no processamento e na microestrutura, além de poder incorporar elementos a esse material para atender às condições de uma determinada aplicação / The humidification, compaction and drying (Umedecimento, Compactação e Secagem UCOS) (1, 2, 3) method produces a high strength material from plaster and water: up to 90 MPa in compression. This work presents the study of mechanical properties of this material and how water, temperature, impurity and microstructure influence in its behavior. During the study of the intercrystalline adhesion force, we found the presence of confined water and that it accounts for great part of the strength. In order to aid the study, another method was developed: Direct Packaging of the Dihydrate (Empacotamento Direto do Dihidrato EDD). In this methodology, it produces a material with the same resistance, but with some difference in the mechanical behavior. Through the high strength reached by the UCOS and EDD methods, the plaster applications can be extended, since the set material by these methods are reliable and safe. In order to evaluate the mechanical properties, the reliability and the safety of these pieces, we performed the study of the fracture mechanics and the fracture toughening mechanisms. In this work, the studied toughening are: microstructure control (enlargement of the fracture surface), polymeric fiber reinforcement (tension distribution on the fracture tip, fracture tip deflection, and fiber bridging), and polymer adhesive reinforcement (they enhance the adhesion between crystals and better distribute the tension on the fracture tip). The results show that the plaster composites of polymeric fibers and/or polymer adhesive have high resistance, and different mechanical behaviors for each type of composite and setting method. Based on the acquired knowledge, we conclude that it is possible to interfere on the processing and on the microstructure, as well as reinforcements in this material to satisfy the needs of a specific application

O método Umedecimento, Compactação e Secagem (UCOS) (1, 2, 3) produz, a partir de gesso e água, um material de elevada resistência mecânica: até 90 MPa na compressão. Este trabalho apresenta o estudo do comportamento mecânico deste material e como a água, a temperatura, as impurezas e a microestrutura influenciam no seu comportamento. Durante o estudo da adesão intercristalina, foi encontrada presença de água confinada e que é responsável por grande parte da resistência mecânica. Para auxiliar o estudo, foi desenvolvido outro método: Empacotamento Direto do Dihidrato (EDD). Nesta metodologia, é produzido um material com a mesma resistência, porém com algumas diferenças no comportamento mecânico diferente. Através da elevada resistência mecânica alcançada pelos métodos UCOS e EDD, as aplicações do gesso podem ser ampliadas desde que o gesso conformado por tais métodos possuam confiabilidade e segurança. Para avaliar as propriedades mecânicas, a confiabilidade e a segurança de tal material, realizou-se o estudo dos mecanismos tenacificadores e da mecânica da fratura. Os mecanismos tenacificadores estudados neste trabalho são: controle da microestrutura (aumento da superfície de ruptura), introdução de fibras poliméricas (distribuição da tensão na ponta da trinca, ramificação da ponta da trinca e contenção da abertura da trinca) e introdução de adesivo polimérico (melhora a adesão entre cristais e distribui melhor a tensão na ponta da trinca). Os resultados mostram que os compósitos de gesso reforçados com fibras poliméricas e/ou adesivo polimérico possuem elevada resistência e comportamentos mecânicos distintos para cada tipo de compósito e método de conformação. Concluímos que, com o conhecimento adquirido, é possível intervir no processamento e na microestrutura, além de poder incorporar elementos a esse material para atender às condições de uma determinada aplicação / The humidification, compaction and drying (Umedecimento, Compactação e Secagem UCOS) (1, 2, 3) method produces a high strength material from plaster and water: up to 90 MPa in compression. This work presents the study of mechanical properties of this material and how water, temperature, impurity and microstructure influence in its behavior. During the study of the intercrystalline adhesion force, we found the presence of confined water and that it accounts for great part of the strength. In order to aid the study, another method was developed: Direct Packaging of the Dihydrate (Empacotamento Direto do Dihidrato EDD). In this methodology, it produces a material with the same resistance, but with some difference in the mechanical behavior. Through the high strength reached by the UCOS and EDD methods, the plaster applications can be extended, since the set material by these methods are reliable and safe. In order to evaluate the mechanical properties, the reliability and the safety of these pieces, we performed the study of the fracture mechanics and the fracture toughening mechanisms. In this work, the studied toughening are: microstructure control (enlargement of the fracture surface), polymeric fiber reinforcement (tension distribution on the fracture tip, fracture tip deflection, and fiber bridging), and polymer adhesive reinforcement (they enhance the adhesion between crystals and better distribute the tension on the fracture tip). The results show that the plaster composites of polymeric fibers and/or polymer adhesive have high resistance, and different mechanical behaviors for each type of composite and setting method. Based on the acquired knowledge, we conclude that it is possible to interfere on the processing and on the microstructure, as well as reinforcements in this material to satisfy the needs of a specific application

This thesis outlines the work done on in-situ synthesis of Al2O3-ZrO2-SiCw ceramic composites and their property evaluation. The introductory chapter deals with the literature survey on ceramic matrix composites, properties desirable for structural applications and toughening mechanisms associated with these composites. The role of whisker toughening in ceramic matrix composites, the growth mechanisms involved in whisker growth and the conditions that favour or hamper the whisker growth are also discussed. The advantages and disadvantages of in-situ synthesis of composites as compared to physical mixing are also dealt with. The objective and scope of the work undertaken are outlined at the end. The second chapter describes the experimental techniques associated with carbothermal synthesis and characterisation of reaction products as well as properties of hot pressed bulk composites. The equipments used for this work are described here. The third chapter focuses on the results obtained by the carbothermal reduction of mixtures of kaolin, sillimanite and zircon taken in various proportions. The formation of the product phases with respect to variations in temperature, variations in composition and effect of catalyst is analysed with the help of XRD while their morphology is analysed using SEM. The conditions favouring the formation of tetragonal zirconia without the addition of stabilizers is also enumerated here. The fourth chapter deals with the compaction of these composite powders and the evaluation of some physical, thermal and mechanical properties. Density and porosity, coefficient of thermal expansion, modulus of rupture and fracture toughness of the composite specimens are evaluated and compared with binary and ternary composites made by other methods. Finally the thesis concludes by summarizing the work done and briefly projecting the areas for future work.

The aim of this study was to investigate rubber toughening of resol type phenol-formaldehyde resin. For this purpose, phenolic resin was first modified by only acrylonitrile butadiene rubber, and then by using nitrile rubber together with 3-aminopropyltriethoxysilane. Test specimens were prepared by mixing and casting of liquid phenolic resin in three groups. In the first one, neat phenolic resin specimens were produced. In the second group, phenolic resin was modified with 0.5, 1, 2, and 3 wt.% nitrile rubber, while in the last group modification was carried out by using 0.5 wt.% nitrile rubber together with 1, 2, and 4wt.% amino silane (with respect to nitrile rubber). All specimens were heat cured in the oven. In order to observe behaviors of the specimens, Three-Point Bending, Charpy Impact, Plane-Strain Fracture Toughness, and Dynamic Mechanical Analysis tests were conducted according to the related ISO standards for all specimens groups. Scanning Electron Microscopy was also used for the fractographic analysis of some samples. It can be concluded that, although there were problems in mixing and casting of liquid resol type phenolic resin, its toughness could be improved by using nitrile rubber and amino silane. Modification by using nitrile rubber and amino silane together was much more effective than by using only nitrile rubber. In this synergistic case for instance, Charpy impact strength and fracture toughness values of the neat phenolic specimens were increased 63% and 50%, respectively. SEM studies indicated that the main rubber toughening mechanism was shear yielding observed as deformation lines especially initiated at the domains of nitrile rubber and amino silane.

Dans cette étude, plusieurs voies ont été explorées dans l’objectif d’utiliser des polyesters aliphatiques issus de ressources oléagineuses comme additifs pour le renfort au choc du poly(L-lactide) (PLLA). Dans un premier temps, des poly(ester-amide)s (PEAs) ont été synthétisés à partir de dérivés de l’huile de ricin. La relation structure-propriétés des PEAs obtenus a été clairement établie. La dispersion des PEAs (à différents taux) par extrusion à l’état fondu dans une matrice de PLLA a ensuite été effectuée, démontrant un accroissement de la résilience de ces mélanges en comparaison au PLLA seul. Une étude systématique reliant la structure d’une large gamme de polyesters aux propriétés des mélanges polyesters/PLLA, a ensuite été réalisée. Une forte dépendance de la résilience des mélanges polyesters/PLLA avec la cristallinité de l’additif polyester a été observée et quantifiée.Une amélioration des propriétés mécaniques du PLLA a également été obtenue par polymérisation par ouverture de cycle du lactide amorcée par un poly(acide ricinoléique) di-hydroxy téléchélique. Les copolymères triblocs ainsi formés ont été caractérisés d’un point de vue morphologique et mécanique.Enfin, un travail exploratoire utilisant l’ADMET comme méthode de polymérisation a été conduit, permettant la synthèse de nouveaux polymères prometteurs pour le renfort au choc du PLLA. Notamment, la copolymérisation de α,ω-diènes bio-sourcés a permis de mimer le polyéthylène basse densité linéaire, couramment employé pour le renfort au choc du PLLA. / The objective of this thesis work, is to promote the use of fatty acid-based aliphatic polyesters as impact modifiers for poly(L-lactide) (PLLA).Firstly, poly(ester-amide)s (PEAs) have been synthesized from castor oil derivatives. The structure-properties relationship of the PEAs so-formed was clearly established. The PEAs were then melt-blended with PLLA by extrusion, yielding blends with improved impact strength compared to neat PLLA.A series of polyesters covering a wide range of thermo-mechanical properties was then employed to evaluate the influence of the polyester morphology on the properties of the blends with PLLA. A strong dependence of the impact strength of the blends was noticed with the crystallinity degree of the polyester additive.An improvement of the mechanical properties of PLLA was also obtained by ring-opening polymerization of lactide initiated by a di-hydroxy telechelic poly(ricinoleic acid). The so-formed triblock copolymers were fully characterized in terms of morphology and mechanical properties.Finally, an exploratory investigation related to the synthesis of PLLA impact modifiers by ADMET was carried out. Particularly, the copolymerization of two bio-based α,ω-dienes yielded a series of “LLDPE like” polyesters, LLDPE being a commonly used impact modifier for PLLA.

Zielsetzung dieser Arbeit war die Zähmodifizierung eines neuen besonders hochtemperaturbeständigen ungesättigten Polyesters, nachfolgend Referenz genannt. Im Rahmen dieser Arbeit wurden verschiedene konzeptionelle Ansätze verfolgt, um die Harz- und Duromer-Eigenschaften von hochtemperaturbeständigen ungesättigten Polyesterharzen (Unsaturated Polyester Resin, UPR) zu modifizieren und zu verstehen.:1. Einleitung 2. Motivation 3. Theoretischer Teil 4. Charakterisierungsmethoden 5. Ergebnisse und Diskussion 6. Zusammenfassung 7. Experimenteller Teil 8. Literaturverzeichnis 9. Anhang 10. Versicherung

La problématique soulevée par la délinquance juvénile, loin de se limiter au pré-carré des professionnels du droit, s’est imposée en véritable débat de société. Cet engouement est le fruit de l’évolution de la délinquance des mineurs, qui a tendance à croître, impliquant des auteurs plus jeunes.En réponse à ce phénomène, le législateur a opéré un tournant sécuritaire en 2002, marquant le point de départ du durcissement des dispositions relatives aux mineurs délinquants, notamment celles applicables à ceux âgés de seize à dix-huit ans. Il en découle un rapprochement du droit pénal des mineurs de celui des majeurs, malgré l’affirmation, la même année, par le Conseil constitutionnel d’un principe fondamental reconnu par les lois de la république qui consacre la spécificité du droit pénal des mineurs. Toutefois, il convient de s’interroger sur la portée de ce rapprochement textuel, qui est peu, voire pas mis en œuvre en pratique. Cette question se pose avec d’autant plus d’acuité depuis le changement de politique pénale impulsé en 2012 par le nouveau garde des Sceaux, qui est d’ailleurs à l’initiative d’un projet de réforme de l’ordonnance de 1945, qui entend réaffirmer la primauté de l’éducatif sur le répressif / Juvenile delinquency problem, far from being the sole issue of law professionals, has become a widely debated topic throughout the entire society. Such interest in the issue takes its roots in the delinquency's evolution, broadly on the rise, with ever younger criminals. Given the phenomenon, the lawmaker has moved towards a harsher approach in 2002, and the various laws have been toughening since then, especially those concerning young people aged between 16 and 18 year old. The consequence is that the body of law applicable to young people looks increasingly similar to that one applicable to adults, despite the solemn statement issued by the Constitutional Council the same year. This statement explains that there is a ground principle deduced from the laws of the Republic, recognizing the specificity of juvenile delinquency laws. It is however interesting to reflect on the true scope of this formal closening, which seems to happen to little or no avail. The issue is even more relevant with the changes in the criminal justice approach advocated by the new secretary of Justice since 2012, who is currently initiating a reform on the body of law applicable to young people, aiming at favoring education over repression

Structural adhesives are widely used with great success, and yet occasional failures can occur, often resulting from improper bonding procedures or joint design, overload or other detrimental service situations, or in response to a variety of environmental challenges. In these situations, cracks can start within the adhesive layer or debonds can initiate near an interface. The paths taken by propagating cracks can affect the resistance to failure and the subsequent service lives of the bonded structures. The behavior of propagating cracks in adhesive joints remains of interest, including when some critical environments, complicated loading modes, or uncertainties in material/interfacial properties are involved. From a mechanics perspective, areas of current interest include understanding the growth of damage and cracks, loading rate dependency of crack propagation, and the effect of mixed mode fracture loading scenarios on crack path selection. This dissertation involves analytical, numerical, and experimental evaluations of crack propagation in several adhesive joint configurations. The main objective is an investigation of crack path selection in adhesively bonded joints, focusing on in-plane fracture behavior (mode I, mode II, and their combination) of bonded joints with uniform bonding, and those with locally weakened interfaces. When removing cured components from molds, interfacial debonds can sometimes initiate and propagate along both mold surfaces, resulting in the molded product partially bridging between the two molds and potentially being damaged or torn. Debonds from both adherends can sometimes occur in weak adhesive bonds as well, potentially altering the apparent fracture behavior. To avoid or control these multiple interfacial debonding, more understanding of these processes is required. An analytical model of 2D parallel bridging was developed and the interactions of interfacial debonds were investigated using Euler-Bernoulli beam theory. The numerical solutions to the analytical results described the propagation processes with multiple debonds, and demonstrated some common phenomena in several different joints corresponding to double cantilever beam configurations. The analytical approach and results obtained could prove useful in extensions to understanding and controlling debonding in such situations and optimization of loading scenarios. Numerical capabilities for predicting crack propagation, confirmed by experimental results, were initially evaluated for crack behavior in monolithic materials, which is also of interest in engineering design. Several test cases were devised for modified forms of monolithic compact tension specimens (CT) were developed. An asymmetric variant of the CT configuration, in which the initial crack was shifted to two thirds of the total height, was tested experimentally and numerically simulated in ABAQUS®, with good agreement. Similar studies of elongated CT specimens with different specimen lengths also revealed good agreement, using the same material properties and cohesive zone model (CZM) parameters. The critical specimen length when the crack propagation pattern abruptly switches was experimentally measured and accurately predicted, building confidence in the subsequent studies where the numerical method was applied to bonded joints. In adhesively bonded joints, crack propagation and joint failure can potentially result from or involve interactions of a growing crack with a partially weakened interface, so numerical simulations were initiated to investigate such scenarios using ABAQUS®. Two different cohesive zone models (CZMs) are applied in these simulations: cohesive elements for strong and weak interfaces, and the extended finite element method (XFEM) for cracks propagating within the adhesive layer. When the main crack approaches a locally weakened interface, interfacial damage can occur, allowing for additional interfacial compliance and inducing shear stresses within the adhesive layer that direct the growing crack toward the weak interface. The maximum traction of the interfacial CZM appears to be the controlling parameter. Fracture energy of the weakened interface is shown to be of secondary importance, though can affect the results when particularly small (e.g. 1% that of the bulk adhesive). The length of the weakened interface also has some influence on the crack path. Under globally mixed mode loadings, the competition between the loading and the weakened interface affects the shear stress distribution and thus changes the crack path. Mixed mode loading in the opposite direction of the weakened interface is able to drive the crack away from the weakened interface, suggesting potential means to avoid failure within these regions or to design joints that fail in a particular manner. In addition to the analytical and numerical studies of crack path selection in adhesively bonded joints, experimental investigations are also performed. A dual actuator load frame (DALF) is used to test beam-like bonded joints in various mode mixity angles. Constant mode mixity angle tracking, as well as other versatile loading functions, are developed in LabVIEW® for use with a new controller system. The DALF is calibrated to minimize errors when calculating the compliance of beam-like bonded joints. After the corrections, the resulting fracture energies ( ) values are considered to be more accurate in representing the energy released in the crack propagation processes. Double cantilever beam (DCB) bonded joints consisting of 6061-T6 aluminum adherends bonded with commercial epoxy adhesives (J-B Weld, or LORD 320/322) are tested on the DALF. Profiles of the values for different constant mode mixity angles, as well as for continuously increasing mode mixity angle, are plotted to illustrate the behavior of the crack in these bonded joints. Finally, crack path selection in DCB specimens with one of the bonding surfaces weakened was studied experimentally, and rate-dependency of the crack path selection was found. Several contamination schemes are attempted, involving of graphite flakes, silicone tapes, or silane treatments on the aluminum oxide interfaces. In all these cases, tests involving more rapid crack propagation resulted in interfacial failures at the weakened areas, while slower tests showed cohesive failure throughout. One possible explanation of this phenomenon is presented using the rate-dependency of the yield stress (commonly considered to be corresponding to the maximum traction) of the epoxy adhesives. These experimental observations may have some potential applications tailoring adhesive joint configurations and interface variability to achieve or avoid particular failure modes. / Ph. D.