L’influence des propriétés microscopiques de l’interphase entre la matrice et les fibres sur le comportement mécanique macroscopique n’est pas suffisamment connue dans le domaine des polymères renforcés par fibres courtes. Dans le cadre de cette thèse, une étude systématique des propriétés géométriques et mécaniques de l’interphase est réalisée concernant la description des effets sur la réponse viscoélastique linéaire du composite. Dans ce contexte, les résultats présentés mettent l’accent sur l’interaction entre la modélisation micromécanique et la caractérisation expérimentale. D’une part, un nouveau modèle micromécanique en deux étapes est développé pour la description d’un composite anisotrope à trois phases avec interphases. D’autre part, les paramètres du matériau utilisés pour la modélisation micromécanique sont identifiés avec des méthodes expérimentales aux échelles micro- et macroscopiques. En comparaison des résultats expérimentaux avec les propriétés effectives calculées de matériau composite, une inférence peut être faite sur les propriétés mécaniques du composite à partir de celles de l’interphase. Par conséquent, une méthode inverse est proposée offrant un accès aux propriétés inconnues de l’interphase. Enfin, la combinaison de la modélisation micromécanique et des résultats expérimentaux permet une meilleure compréhension des propriétés mécaniques de l’interphase, qui n’étaient auparavant pas accessibles au moyen de seules approches expérimentales / In order to improve the mechanical properties of short fiber composites, the fiber-matrix adhesion is decisive and depends strongly on the intersection region between the fiber and the matrix material. However, no perspicuous information about the influence or mechanical properties of the fiber-matrix interphase in short fiber reinforced thermoplastic composites is available. Thus, the present thesis aims for a systematic identification of the geometrical and mechanical impacts of an interphase on the linear-viscoelastic behavior in short glass fiber reinforced thermoplastics. Thereby, the performed investigations are focused on the interaction between micromechanical material modeling and experimental testing. On the one hand, a two-step modeling approach is developed for the realistic description of an entire three phase composite with interphase including anisotropic and linear-viscoelastic effects. On the other hand, the input of this model is provided by different experimental testing methods ranging from the micro- to the macroscale characterization of the composite and matrix material. By comparing these experimental results with the linear-viscoelastic modeling output, the impact of the interphase on the mechanical properties of the composite is accessible. Thus, it is shown that a realistic material modeling and experimental investigations are closely interlinked

Cette thèse s’inscrit dans le cadre d’un projet GREENANONANO né d’un partenariat entre le Luxembourg Institute of Science and Technology (LIST), Goodyear et l’Université de Lorraine dans le but de relever un défi technologique concernant l’augmentation des performances des propriétés viscoélastiques de la gomme utilisée dans les pneumatiques. Cette gomme est un composite constitué d’un élastomère (caoutchouc naturel) renforcé par la silice et le noir de carbone. La dispersion de ces charges n’est pas optimale et tend à dégrader les propriétés mécaniques et électrostatiques et donc les performances des pneus. Faces à ces limitations industrielles, l’utilisation d’autres types de renforts tels que les nanotubes de carbone devient une alternative crédible. Etant donné que les nanotubes de carbone (NTCs) ont tendance à s’organiser en fagots, le problème de la dispersion reste à résoudre. Nous proposons dans cette thèse la mise en place d’un matériau biphasé constitué de silice mésoporeuse naturelle, appelée diatomite, sur laquelle ont été synthétisés des NTCs. La grande surface spécifique de la diatomite offre la possibilité d’y faire croître une grande densité de NTCs et d’accroître significativement la surface de contact avec la matrice polymère. Cette thèse multidisciplinaire a débuté par la synthèse de nanoparticules métalliques par ALD pour la croissance de NTCs, suivie d’un développement du procédé de croissance de NTCs sur la diatomite. L’intégration réussie des charges biphasées obtenues au sein de matrices polymériques (élastomère, thermoplastique) a permis de mesurer les propriétés mécaniques, thermiques et électriques des nanocomposites ainsi fabriqués / This thesis is part of the GREENANONANO project ensuing from a partnership between the Luxembourg Institute of Science and Technology (LIST), Goodyear Company and Université de Lorraine, in order to address a technological challenge for increasing tires performances. The latter are directly related to the viscoelastic properties of the rubber used in tires. This gum is a composite material made by mixing an elastomeric matrix (natural rubber) and fillers (silica and carbon black). Nowadays, the filler dispersion is not optimal, which degrades the mechanical and electrostatic properties and therefore performances of tires. All these industrial limitations require the use of other types of reinforcing agents such as carbon nanotubes. Since carbon nanotubes tend to be organized into bundles, the dispersion problem still exists. We therefore propose in this thesis the synthesis of a biphased material composed by diatomite particles (natural mesoporous silica) on which are grown carbon nanotubes (CNTs). The high surface area of diatomite offers the possibility of growing a high density of CNTs, increasing the contact area with the polymer matrix. This multidisciplinary thesis started with the synthesis of metal nanoparticles by Atomic Layer Deposition (ALD) to catalyse the growth of CNTs and then a process was developed to grow CNTs on diatomite particles. The successful integration of the resulting biphased particles in polymer matrices (elastomer, thermoplastic) allowed to measure the mechanical, thermal and electrical properties of the nanocomposites thus produced

abstract: There are many applications for polymer matrix composite materials in a variety of different industries, but designing and modeling with these materials remains a challenge due to the intricate architecture and damage modes. Multiscale modeling techniques of composite structures subjected to complex loadings are needed in order to address the scale-dependent behavior and failure. The rate dependency and nonlinearity of polymer matrix composite materials further complicates the modeling. Additionally, variability in the material constituents plays an important role in the material behavior and damage. The systematic consideration of uncertainties is as important as having the appropriate structural model, especially during model validation where the total error between physical observation and model prediction must be characterized. It is necessary to quantify the effects of uncertainties at every length scale in order to fully understand their impact on the structural response. Material variability may include variations in fiber volume fraction, fiber dimensions, fiber waviness, pure resin pockets, and void distributions. Therefore, a stochastic modeling framework with scale dependent constitutive laws and an appropriate failure theory is required to simulate the behavior and failure of polymer matrix composite structures subjected to complex loadings. Additionally, the variations in environmental conditions for aerospace applications and the effect of these conditions on the polymer matrix composite material need to be considered. The research presented in this dissertation provides the framework for stochastic multiscale modeling of composites and the characterization data needed to determine the effect of different environmental conditions on the material properties. The developed models extend sectional micromechanics techniques by incorporating 3D progressive damage theories and multiscale failure criteria. The mechanical testing of composites under various environmental conditions demonstrates the degrading effect these conditions have on the elastic and failure properties of the material. The methodologies presented in this research represent substantial progress toward understanding the failure and effect of variability for complex polymer matrix composites. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2016

abstract: Composite materials are now beginning to provide uses hitherto reserved for metals in structural systems such as airframes and engine containment systems, wraps for repair and rehabilitation, and ballistic/blast mitigation systems. These structural systems are often subjected to impact loads and there is a pressing need for accurate prediction of deformation, damage and failure. There are numerous material models that have been developed to analyze the dynamic impact response of polymer matrix composites. However, there are key features that are missing in those models that prevent them from providing accurate predictive capabilities. In this dissertation, a general purpose orthotropic elasto-plastic computational constitutive material model has been developed to predict the response of composites subjected to high velocity impacts. The constitutive model is divided into three components – deformation model, damage model and failure model, with failure to be added at a later date. The deformation model generalizes the Tsai-Wu failure criteria and extends it using a strain-hardening-based orthotropic yield function with a non-associative flow rule. A strain equivalent formulation is utilized in the damage model that permits plastic and damage calculations to be uncoupled and capture the nonlinear unloading and local softening of the stress-strain response. A diagonal damage tensor is defined to account for the directionally dependent variation of damage. However, in composites it has been found that loading in one direction can lead to damage in multiple coordinate directions. To account for this phenomena, the terms in the damage matrix are semi-coupled such that the damage in a particular coordinate direction is a function of the stresses and plastic strains in all of the coordinate directions. The overall framework is driven by experimental tabulated temperature and rate-dependent stress-strain data as well as data that characterizes the damage matrix and failure. The developed theory has been implemented in a commercial explicit finite element analysis code, LS-DYNA®, as MAT213. Several verification and validation tests using a commonly available carbon-fiber composite, Toyobo’s T800/F3900, have been carried and the results show that the theory and implementation are efficient, robust and accurate. / Dissertation/Thesis / Doctoral Dissertation Civil and Environmental Engineering 2016

The increasing demand for polymer matrix composites (PMCs) from the airframe industry raises the issues of productivity, cost and reproducibility of manufactured PMC components. Performance reproducibility is closely related to the manufacturing technique. Resin transfer moulding (RTM) offers the advantage of flexible manufacturing of net-shape PMC components with superior repeatability starting from ready-to-impregnate dry reinforcements. An RTM apparatus was developed for manufacturing PMC plates and demonstrator components representative of actual, PMC components and PMC moulds made and used in the airframe industry. The RTM process developed in this work involved making net-shape dry carbon fibre preforms and impregnating them an epoxy resin, targeting mould applications. Thermal repeatability of different net-shape PMC components manufactured using the RTM apparatus developed in-house was investigated. Effects of bonding an outer copper plate onto the PMC material, targeting mould applications known as integrally heated copper tooling (IHCT), were explored. Heat conduction through the PMC components was studied using simulation models validated by experimental data obtained primarily by thermography. Manufactured PMC components showed good repeatability, particularly in terms of thermal behaviour. The IHCT technique was found to be well suited for mould applications. Expected advantages of thermography were materialised. Finally, the simulation models developed were in good agreement with experimental data.

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No description available.

Polymer matrices are commonly used as guest-host systems for organic chromophores for use in non-linear optical materials. The chromophores must be aligned or poled in an electric field in order to impart anisotropy and non-linear activity to the material. This poling process raises several issues, the two largest being the eventual relaxation of the chromophores back into random orientations due to brownian motion, and high molecular weight polymer matrices limiting chromophore mobility during poling. The prevention of this relaxation process is an area of significant interest, especially in applications that require long term coating stability and activity. In this study, a polymer matrix is synthesized that seeks to solve both of these problems with one system. The ideal system would be one that allows for chromophore mobility during processing, but once chromophores have reached the desired orientation, limits mobility and relaxation during in-service usage. A copolymer of methyl methacrylate and a Diels-Alder adduct cross-linking monomer was synthesized in order to meet these challenges. This polymer was blended with commercially available acrylic polymer and organic chromophore molecules in order to test the viability of the solution. It was found that at the percent composition of cross-linker being utilized in the study, the Diels-Alder linkages were not reforming in any measurable amount due to the low amount of Diels-Alder active monomer units. This led to the development of a new system based on mixing polyfuran based polymers with polymaleimide based polymers during processing. This method allows for high amounts of cross-linking after processing ceases, which achieves both initial goals of the project, as well as allowing facile synthesis of the desired polymer components. Another attempt to address these issues in polymer matrix formation led to the use of a novel inimer system. The cross-linking agent was also the polymerization initiator, and these functionalities were separated by a Diels-Alder linkage that would fall apart upon exposure to thermal stimulus. These polymers were synthesized and isolated easily, although in some cases gelation occurred. In order to observe the extent of the cross-linking inimer being incorporated into the matrix, cleavage experiments were performed to induce the breaking of the Diels-Alder adduct. Analyzing the Diels-Alder cleaved polymer led to an interesting result: all polymers showed an increase in apparent molecular weight when analyzed by gel permeation chromatography. The increase in molecular weight occurring upon cleavage of main chain bonds has never before been observed in literature. The explanation proposed was that the polymer adopted a "ropeball" like topology consisting of tightly coiled loops and knots. Upon cleavage of the cross-links, the ropeball was able to unwind into a much more linear topology, occupying a much larger hydrodynamic volume. This increase in hydrodynamic volume would cause the gel permeation chromatography results to show an apparent increase in molecular weight.

Yes / Composites have clinical application for their ability to mimic the hierarchical structure of human tissues. In tissue engineering applications the use of degradable biopolymer matrices reinforced by bioactive ceramics is seen as a viable process to increase osteoconductivity and accelerate tissue regeneration, and technologies such as additive manufacturing provide the design freedom needed to create patient-specific implants with complex shapes and controlled porous structures. In this study a medical grade poly(l-lactide) (PLLA) was used as matrix while apatite-wollastonite (AW) was used as reinforcement (5 wt% loading). Premade rods of composite were pelletized and processed to create a filament with an average diameter of 1.6 mm, using a twin-screw extruder. The resultant filament was 3D printed into three types of porous woodpile samples: PLLA, PLLA reinforced with AW particles, and PLLA with short AW fibres. None of the samples degraded in phosphate buffered solution over a period of 8 weeks, and an average effective modulus of 0.8 GPa, 1 GPa and 1.5 GPa was obtained for the polymer, particle and fibre composites, respectively. Composite samples immersed in simulated body fluid exhibited bioactivity, producing a surface apatite layer. Furthermore, cell viability and differentiation were demonstrated for human mesenchymal stromal cells for all sample types, with mineralisation detected solely for biocomposites. It is concluded that both composites have potential for use in critical size bone defects, with the AW fibre composite showing greater levels of ion release, stimulating more rapid cell proliferation and greater levels of mineralisation. / The research was funded in part by the UK EPSRC Centre for Doctoral Training in Additive Manufacturing and 3D Printing (EP/L01534X/1), the UK EPSRC Centre for Innovative Manufacture in Medical Devices (EP/K029592/1), and Glass Technology Services Ltd., Sheffield, UK.

No description available.