Ulm, Univ. Diss., 2006.

Les réservoirs composites de type IV utilisés pour le stockage de l’hydrogène gazeux rencontrent du succès dans les applications mobiles de la pile à combustible. Au cours de leur utilisation, ces supports de stockage sont soumis à des cycles successifs de remplissage/maintien/vidange en hydrogène. Sous des conditions spécifiques de vidange, l’apparition d’un décollement entre l’enveloppe en polyamide 6 qui assure l’étanchéité (liner) et la paroi composite, peut être observée. Ce décollement, encore appelé collapse, peut poser des problèmes de limitation à un débit de vidange lent ou à un seuil minimal de pression résiduelle du gaz sur le liner.Air Liquide a cherché à élucider expérimentalement l’influence des cycles de pression en hydrogène sur le comportement mécanique des liners en situation de collapse. Mais compte tenu des coûts très élevés des essais, l’utilisation d’un outil numérique prédictif s’avérait nécessaire. L’enjeu principal dans le développement d’un tel outil était la modélisation du comportement d’un liner collapsé sous des chargements de cyclage – fluage.L’objectif de cette thèse est de proposer une loi de comportement capable de prédire l’évolution cyclique de la déformée d’un liner en situation collapsée.Le liner est exposé à plusieurs variations de son environnement : présence d’un résidu d’humidité dans le liner après épreuve hydraulique, variations de températures générées par la compression/détente de l’hydrogène, diffusion de l’hydrogène dans le liner. Un travail préliminaire a donc consisté à évaluer l’influence de ces différents facteurs environnementaux sur la réponse mécanique du polyamide 6. Cette première étape a permis de définir un cadre de sollicitation à l’échelle du laboratoire, mais qui préserve les principales caractéristiques du collapse. Les essais de caractérisation sur éprouvette ont montré que le liner pouvait être modélisé par une loi viscoélastique multiaxiale formulée dans le cadre thermodynamique des processus irréversibles en petites déformations, faiblement couplée avec la thermique. Des modifications mineures ont été introduites pour permettre à cette loi de capter les effets du comportement en fatigue-fluage d’un liner en situation collapsé. Ces modifications ont malheureusement pénalisé l’identification manuelle et par conséquent, ont conduit à développer une stratégie d’identification spécifique. La qualité de d’identification a été évaluée dans le cadre isotherme en regardant les effets de la vitesse de la sollicitation, du niveau de contrainte et de la température. Puis, le modèle a été validé en présence de transitoires thermiques, d’abord sur éprouvette, ensuite dans un réservoir en présence d’un collapse. / Hyperbaric hydrogen storage vessels of type IV are encountering success for portable applications of fuel cell. During their use, these cylindric containers undergo repeated fill in/fill out cycles of H2-gaz. Under specific fillout conditions, an emerging detachment between the sealing inner layer (liner) and the composite wall, can be observed. This layer debonding also called collapse may limit the pressure release rate of H2-vessels or increase the residual gas pressure prescribed to avoid collapse.Experimental studies have been conducted by Air Liquide at vessel scale to identify some parameters responsible for the collapse onset. But the high cost of these studies and the complexity of the operating conditions makes the use of numerical tools necessary. That led to a numerical modeling approach. The main goal in the numerical approach is to model the cyclic mechanical response of a collapsed liner under fatigue – creep loadings.In this thesis, the purpose was to develop a mechanical constitutive law able to predict the cyclic deformation of a collapsed liner subjected to hydrogen pressure cycles.The liner was subjected to several environment variations due to: (i) the presence of residual water into the liner after initial hydraulic vessel tests, (ii) the temperature changes caused by the hydrogen compression/expansion, and (iii) the hydrogen diffusion/saturation. So, a preliminary work consisted in investigating the influence of each environmental factor on the polyamide 6 mechanical response. This first step allowed to outline a loading frame at laboratory scale that preserved main characteristics of the collapse phenomenon. Characterization tests on tensile specimens revealed that the liner could be modelled by a non linear viscoelastic law written within the thermodynamic framework of the irreversible processes in small deformations, and coupled with the temperature. Minor changes were introduced to extend the model capacity to capture liner behavior effects during fatigue – creep. These changes had negative impact on the manual method of model calibration, and consequently required to develop a specific identification strategy. The identification performance was assessed in different isothermal frames through stress rate, stress level and temperature effects. Then, the calibrated model was validated by taking temperature gradients into account, firstly on a tensile specimen, secondly within a H2-vessel.

Dynamic loading of polycrystalline metallic materials can result in brittle or ductile fracture depending on the loading rates, geometry, and material type. At high strain rates, mechanical energy due to plastic deformation may lead to significant temperature rise and shear localization due to thermal softening. These shear bands reduce the stress-bearing capacity of the material and act as a precursor to ductile fracture (e.g. cracks that develop rapidly on top of a shear band). Reliable models are needed to predict the response of metals subject to dynamic loads. Understanding the heat transfer physics in thermo-mechanical problems when cracks are developed is of great importance. In particular, capturing the interplay between heat conduction and crack propagation is still an open research field. To accurately capture the heat transfer physics across crack surfaces, damage models degrading thermal-conductivity are necessary. In this thesis, a novel set of isotropic thermal-conductivity degradation functions is derived based on a micro-mechanics void extension model of Laplace's equation. The key idea is to employ an analytical homogenization process to find the effective thermal-conductivity of an equivalent sphere with an expanding spherical void. The closed-form solution is obtained by minimization of the flux differences at the outer surfaces of the two problems, which can be achieved using the analytical solution of Laplace's equations, so-called spherical-harmonics. Additionally, a new anisotropic approach is proposed in which thermal-conductivity, which depends on the phase-field gradient, is degraded solely across the crack. We show that this approach improves the near-field approximation of temperature and heat flux compared with isotropic degradation when taking the discontinuous crack solutions as reference. To demonstrate the viability of the proposed (isotropic and anisotropic) approaches, a unified model, which accounts for the simultaneous formation of shear bands and cracks, is used as a numerical tool. In this model, the phase-field method is used to model crack initiation and propagation and is coupled to a temperature-dependent visco-plastic model that captures shear bands. Benchmark problems are presented to show the necessity of the anisotropic thermal-conductivity approach using physics-based degradation functions in dynamic fracture problems. On the other hand, the computational burden in dynamic fracture problems with localized solution features is highly demanding. Iterative methods used for their analysis often require special treatment to be more efficient. Specifically, the nonlinear thermomechanical problems we study in this thesis lead to strain localizations, such as shear bands and/or cracks, and iterative solvers may have difficult time converging. To address this issue, we develop a novel updating domain decomposition preconditioner for parallel solution of dynamic fracture problems. The domain decomposition method is based on the Additive Schwarz Method (ASM). The key idea is to decompose the computational domain into two subdomains, a localized subdomain that includes all localized features of the solution and a healthy subdomain for the remaining part of the domain. In this way, one can apply different solvers in each subdomain, i.e. focus more effort in the localized subdomain. In this work, an LU solver is applied in both subdomains, however, while the localized subdomain is solved exactly at every nonlinear iteration, the healthy subdomain LU operator is reused and only selectively updated. Hence, significant CPU time savings associated with the setup of the preconditioner can be achieved. In particular, we propose a strategy for updating the preconditioner in the healthy subdomain. The strategy is based on an idealized performance-based optimization procedure that takes into account machine on-the-fly execution time. Three dynamic fracture problems corresponding to different failure modes are investigated. Excellent performance of the proposed updating preconditioner is reported in serial and parallel simulations.

A tetrazole is a 5-membered ring containing 4 nitrogens and 1 carbon. Due to its energetic potential and structural similarity to carboxylic acids, this ring system has a wide number of applications. In this thesis, a new and safe sustainable process to produce tetrazoles was designed that acheived high yields under mild conditions. Also, a technique was developed to form a trityl-protected tetrazole in situ. The rest of this work involved the exploitation of the energetic potential of tetrazoles. This moiety was successfully applied in polymers, ionic liquids, foams, and gels. The overall results from these experiments illustrate the fact that tetrazoles have the potential to serve as a stable alternative to the troublesome azido group common in many energetic materials. Due to these applications, the tetrazole moiety is a very important entity.

M. Tech. Polymer Technology. / Studies the effects of incorporating epoxidised soybean oil (ESO) in a standard bisphenol A-type epoxy resin (EP) cured by both amine and anhydride hardeners. The EP/ESO ratio was set for 100/0, 75/25, 50/50, 25/75 and 0/100 (wt./wt.). The investigations performed covered the curing, rheology (gelling), and thermomechanical analysis and thermogravimetric analysis of the sample produced.

The first part of the dissertation focuses on understanding and modeling the conduction mechanism of conductive adhesives. The contact resistance is measured between silver rods with different coating materials, and the relationship between tunnel resistivity and contact pressure is obtained based on the experimental results. Three dimensional microstructure models and resistor networks are built to simulate electrical conduction in conductive adhesives. The bulk resistivity of conductive adhesives is calculated from the computer-simulated model. The effects of the geometric properties of filler particles, such as size, shape and distribution, on electrical conductivity are studied by the method of factorial design. The second part of the dissertation evaluates the reliability and investigates the failure mechanism of conductive adhesives subjected to fatigue loading, moisture conditioning and drop impacts. In fatigue tests it is found that electrical conduction failure occurs prior to mechanical failure. The experimental data show that electrical fatigue life can be described well by the power law equation. The electrical failure of conductive adhesives in fatigue is due to the impaired epoxy-silver interfacial adhesion. Moisture uptake in conductive adhesives is measured after moisture conditioning and moisture recovery. The fatigue life of conductive adhesives is significantly shortened after moisture conditioning and moisture recovery. The moisture accelerates the debonding of silver flakes from epoxy resin, which results in a reduced fatigue life. Drop tests are performed on test vehicles with conductive adhesive joints. The electrical conduction failure happens at the same time as joint breakage. The drop failure life is found to be correlated with the strain energy caused by the drop impact, and a power law life model is proposed for drop tests. The fracture is found to be interfacial between the conductive adhesive joints and components/substrates. This research provides a comprehensive understanding of the conduction mechanism of conductive adhesives. The computer-simulated modeling approach presents a useful design tool for the conductive adhesive industry. The reliability tests and proposed failure mechanisms are helpful to prevent failure of conductive adhesives in electronic packages. Moreover, the fatigue and impact life models provide tools in product design and failure prediction of conductive adhesives.

Porous ceramic-metal composites, or cermets, such as nickel zirconia (Ni-YSZ), are widely used as the anode material in solid oxide fuel cells (SOFC). These materials need to enable electrochemical reactions and provide the mechanical support for the layered cell structure. Thus, for the anode supported planar cells, the thermomechanical behavior of the porous cermet directly affects the reliability of the cell. Porous cermets can be viewed as three-phase composites with a random heterogeneous microstructure. While random in nature, the effective properties and overall behavior of such composites can still be linked to specific stochastic functions that describe the microstructure. The main objective of this research was to develop the relationship between the thermomechanical behavior of porous cermets and their random microstructure. The research consists of three components. First, a stochastic reconstruction scheme was developed for the three-phase composite. From this multiple realizations with identical statistical descriptors were constructed for analysis. Secondly, a finite element model was implemented to obtain the effective properties of interest including thermal expansion coefficient, thermal conductivity, and elastic modulus. Lastly, nonlinear material behaviors were investigated, such as damage, plasticity, and creep behavior. It was shown that the computational model linked the statistical features of the microstructure to its overall properties and behavior. Such a predictive computational tool will enable the design of SOFCs with higher reliability and lower costs.

Les composites à matrice polymère sont de plus en plus utilisés dans le secteur automobile. Afin de remplir les conditions exigeantes du cahier des charges vis-à-vis des conditions de mise en service, les pièces en composite doivent maintenir leur forme géométrique sous des conditions thermo-mécaniques parfois extrêmes. Par exemple, un assemblage de hayon composite est soumis à des contraintes mécaniques élevées associées à des variations de température importantes lors des essais de validation du cahier des charges. Les enjeux de la thèse sont axés sur l’aide à la conception dans le domaine quasi-statique de pièces industrielles injectées en thermoplastique renforcé de fibres discontinues. L’amélioration des outils numériques doit permettre un dimensionnement virtuel optimal de ces pièces en anticipant les variations rencontrées en service et les distorsions résiduelles résultantes de chargements thermo-mécaniques. Cette démarche s’appuie sur la connaissance du comportement thermo-mécanique du matériau de l’étude, celui du renfort de hayon, un polypropylène renforcé à 40% en masse de fibres de verre discontinues, et sur la modélisation du comportement de ce type de matériau. / Discontinuous fibers reinforced thermoplastic materials have been widely used for several years in the automotive industry. These parts must resist demanding service life conditions and must meet thermo- mechanical specifications. Indeed, structural automotive spare parts have to endure high temperatures, like a few tens of degrees Celsius, for a long duration, at least a few hours. As an example, a structural part of tailgate is subject to high mechanical loading, associated to strong temperature variations, during the validation test, regarding specifications. The purpose of this work is to improve the design of complex industrial parts, like the tailgate in quasi-static domain, by relying on numerical simulation. One of the challenges related to the use of such material, is to have a reliable virtual design of industrial parts by predicting the geometrical variations during service life conditions, and residual strain. Therefore, it is necessary to characterize and to model the thermo-mechanical behavior of the tailgate material, a polypropylene matrix reinforced with discontinuous glass fibers, with a given mass fraction of 40%

The thermomechanical properties of monolayer graphene and the interfacial interactions between graphene and an SiO₂ substrate are investigated in this dissertation using a multiscale approach. The temperature dependent mechanical behavior of graphene with thermal fluctuations is studied by statistical mechanics analysis under harmonic approximation, which is then compared to molecular dynamics simulations. It is found that the amplitude of thermal fluctuation depends nonlinearly on the graphene size due to anharmonic interactions between bending and stretching modes, but a small positive pre-strain could suppress fluctuation amplitude considerably and results in very different scaling behavior. The thermal expansion of graphene depends on two competing effects: positive expansion due to in-plane modes and negative expansion due to out-of-plane fluctuations. The in-plane stress-strain relation of graphene becomes nonlinear even at infinitesimal strain due to the entropic contribution. Consequently, the modulus of graphene depends on strain non-monotonically, with strain stiffening followed by intrinsic softening. Moreover, it is found that the thermomechnical behavior of graphene is dependent on its interactions with environment such as supporting substrate. The interfacial interactions between graphene and SiO₂ substrate is investigated in terms of three perspectives. Firstly, the interaction mechanisms between graphene and SiO₂ substrate are studied by density functional theory (DFT). The dispersion interaction is found to be the predominant mechanism, and the interaction strength is strongly influenced by changes of SiO₂ surface structures due to surface reactions with water. The adhesion energy is reduced when the reconstructed SiO₂ surface is hydroxylated, and further reduced when covered by a monolayer of adsorbed water molecules. Next, we study the interfacial interactions between graphene and a wet substrate that is covered by a liquid-like water film. During the separation of graphene from the wet substrate, MD simulations show evolution of the water from a continuous film to discrete islands. The water bridging effects are further described by continuum models. Finally, a continuum model is developed to predict how the surface roughness may affect the adhesion between graphene membranes and their substrate. / text

Les besoins en électronique de puissance, de plus en plus exigeants, ont motivé des recherches à l'échelle mondiale sur d'autres matériaux tels que le diamant comme remplaçant du silicium. Nos travaux de recherche sont plus spécifiquement axés sur la définition et la qualification de matériaux polymères capables de garantir l'intégrité des fonctions physiques de modules de puissance en environnement sévère. L'étude concerne la durabilité de candidats polymères à retenir pour le boîtier dont l'objectif est de protéger l'interrupteur de l'environnement extérieur. Suite aux choix des différents polymères étudiés, variables dans leur chimie et leur morphologie (amorphe ou semi-cristallin), un premier objectif scientifique est alors de chercher les relations structures/propriétés permettant de contrôler le procédé de mise en forme des polyimides semi-cristallins et d'en déduire les conditions requises à l'obtention de performances optimisées. Un second objectif a concerné la tenue des différents matériaux sélectionnés en vieillissements isothermes thermo-oxydatifs. / Requirements in power electronics are more and more demanding about materials behavior in their operating conditions. This has motivated global scale researches about other materials replacing silicon such as diamond. This study is specifically focusing on the definition and qualification of polymer materials which could preserve physical functions of power modules in severe environments. This study focuses on the durability of several polymers used for the case. This later allows to protect the chip from external environment. The choice of different studied polymers which are dissimilar in chemistry and morphology (i.e. amorphous or semicrystalline) has been made in this study. Then, a first scientific goal was to search the structures/properties relations leading to the control of the manufacturing process of semicrystalline polyimides. A second goal concerned the mechanical strength evaluation of selected materials after thermo-oxidative isothermal ageing.