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NR 20140805

This research has focused on understanding the mechanicPhysics and chemistry based constitutive framework for thermo-chemo-mechanical responses of polymeric materialsPhysics and Chemistry Based Constitutive Framework for Thermo-Chemo-Mechanical Responses of Polymeric Materialss and multi-physics of soft materials with rate-and temperature-dependent matrices. Such materials are oftentimes exposed to extreme environmental conditions such as Ultra-Violet (UV) light, elevated temperatures, and oxygen which degenerate their mechanical properties and contribute to their permanent failure. The irreversible changes in the mechanical response of polymers induced by such deleterious processes is commonly referred to as polymer aging. The ultimate goal of this work has been to identify the relevant damage processes affecting the lifetime of polymeric materials, and to develop predictive physics- and chemistry-based, thermodynamically consistent constitutive frameworks to evaluate their response under extreme environmental condition. A series of interconnected experimental, theoretical, and numerical studies were developed regarding the chemical, morphological, and mechanical changes that polymers and elastomers exhibit under thermo-photo-chemo-mechanical conditions. Emphasis was placed on linking the aggravation of macrostructural changes (such as cross-link breakage/formation and transformation of linkages) to the macromechanical response of aged polymers, and the development of a mathematically verifiable procedure for incorporating stored and dissipated energies – obtained through chemical experiments – into the thermodynamic formalism. Fracture was considered using the phase-field approach to brittle failure through development of robust and efficient numerical algorithms intended to solve the highly coupled and nonlinear displacement-damage problems. Results demonstrate that several chemical characterization tests such as equilibrium swelling, differential scanning calorimetry (DSC), quartz crystal microbalance with dissipation (QCMD-D), and dynamic mechanical analysis (DMA) can indeed reveal crucial information regarding the physio-chemical changes manifested within polymer networks. Information obtained from these tests can then be employed to propose accurate predictive evolution functions for the mechanical as well as the fracture properties towards a complete physics- and chemistry-based constitutive framework. Numerical analyses were performed within finite element software Abaqus via several user-element and user-material subroutines (UEL, VUMAT) to investigate the predictive capabilities of the developed frameworks in describing complex loading configurations including fracture. The developed constitutive frameworks are all thermodynamics-based and rely solely on the outputs obtained through appropriate chemical characterization techniques. Not only are the predicted results highly accurate, but also and most importantly, the developed constitutive equations are completely self-contained and bypass the need for extra fitting variables. / Doctor of Philosophy / Material science is a fundamental field of research. Understanding how materials behave under various operating conditions can help scientists and engineers propose efficient and economical designs with the aim of potentially establishing a robust foundation for our infrastructure. This work focused on the study and prediction of the deleterious effects of several environmental factors such as elevated temperature, Ultra-Violet (UV) light, and oxygen on the mechanical and failure responses of polymer systems. Several interconnected experimental, theoretical, and numerical studies were developed with the aim of characterizing the chemical, morphological, and mechanical changes that such material systems exhibit under coupled dissipation phenomena. In particular, this research aimed to investigate the aggravation of macrostructural changes that manifested themselves within polymer systems upon exposure to thermo-oxidation and photo-oxidation. Predictive constitutive frameworks were developed based on principles of thermodynamics and continuum damage theories to understand the effects that heterogeneous aging has on the mechanical and fracture responses of these materials. Results achieved in this work helped fill several gaps on both the theoretical as well as numerical sides towards a complete physics and chemistry-based constitutive framework for the analysis of multi-physics phenomena in soft materials. Overall, results shed light on our understanding of the aging process and the predictive capabilities of our proposed equations in describing such degenerative processes as thermo-chemo-mechanical aging. Findings from this work will contribute to the design of high-performance polymers in other applications such as implanted bio-medical devices. Ultimately, describing aging under extreme environmental conditions will contribute to the understanding and prediction of plastic fragmentation processes and therefore, microplastic pollution.

The use of plastic materials in the design of vehicle components is primarily driven by the need for vehicle weight and cost reduction. Additionally, these materials give design engineers freedom in creating appealing exterior designs. However, creating self-carrying exterior structures with polymers must fulfill long-term strength, creep and fatigue life requirements. Thus, the polymer polyDicyclopentadiene (pDCPD) has been chosen for this purpose. Its aging mechanics need to be understood by the design engineers to make the right decisions. This thesis has carried out mechanical tests such as uniaxial tensile testing, fatigue, and creep testing. Digital image correlation (DIC) system has been used to capture strain data from tensile tests. In the final analysis, DIC measurements proved more accurate than extensometer data retrieved from the testing machine. The rise in temperature has been captured using thermal imaging. Several degradation processes have been explored including physical aging, thermo-oxidation, photo-oxidation, chemical- and bio- degradations. Test results showed significant changes in mechanical properties after 17 years of aging. Additionally, severe thermal degradation has been observed in one of the tested panels of pDCPD. Temperature can rise to significant levels during cyclic loading at high stresses, which could have an impact on physical aging effects. Viscoelastic behavior has been explored and changes in dynamic and creep properties have been observed. The investigation also reviled that different defects caused by flawed manufacturing also can affect the material severely as one case has proved in this research.

Les travaux entrepris dans le cadre de cette thèse portent sur l’étude de la représentativité du vieillissement thermique accéléré par rapport au vieillissement en conditions d’usage de mélanges de polyéthylènes utilisés comme isolant de câbles qualifiés K1 de dernière génération dans les bâtiments réacteurs des centrales nucléaires. L’influence de l’état physique des constituants du mélange pendant le vieillissement sur les cinétiques et les mécanismes de vieillissement est également étudiée. Le matériau est un mélange de deux polyéthylènes : un polyéthylène linéaire (PE) et un polyéthylène ramifié (PEcB) réticulé au peroxyde. Une approche basée sur l’analyse multi-échelle (moléculaire, microstructurale, macromoléculaire et macroscopique) a été mise en place. Plusieurs températures de vieillissement ont été choisies afin de faire varier l’état physique de l’un ou des deux polyéthylènes du mélange au cours du vieillissement. Les résultats à l’échelle moléculaire montrent les mêmes produits d’oxydation et les mêmes cinétiques pour le PE et le PEcB. En revanche, on observe une oxydation plus rapide du mélange 5050. Les cinétiques d’oxydation obéissent à une loi d’Arrhenius pour des vieillissements compris entre 80°C et 110°C, mais l’extrapolation à la température d’utilisation (60°C) n’est pas représentative du résultat expérimental. L’état physique (solide ou fondu) des échantillons au moment du vieillissement n’explique pas la non-représentativité des vieillissements accélérés. Les variations des propriétés mécaniques peuvent être reliées à l’évolution de la microstructure de chaque polymère et de leur architecture macromoléculaire au cours du vieillissement thermo-oxydant. Néanmoins, il apparaît difficile de corréler l’évolution de la structure chimique au cours du vieillissement avec l’évolution des propriétés mécaniques. Cette étude souligne l’importance de l’approche multi-échelle pour avoir une compréhension globale des phénomènes de vieillissement. / This work is devoted to the study of the representativeness of accelerated thermal ageing compared to ageing in use conditions of polyethylene blends used as insulant in the lastest-generation K1 qualified cables in nuclear power plants’ reactor buildings. The influence of the physical state of the components in the blends during ageing on the kinetics and ageing mechanisms is also studied. The material is a blend of two polyethylenes: a linear polyethylene (PE) and a branched polyethylene (PEcB) crosslinked with peroxides. An approach based on the multi-scale analysis (molecular, microstructural, macromolecular and macroscopic) was set up. Several ageing temperatures were chosen in order to vary the physical state of one or both polyethylenes in the blend during ageing. The results at molecular scale show the same oxidation products and kinetics for PE and PEcB. However, one can observe a faster degradation for the 5050 blend. The oxidation kinetics obey the Arrhenius law for thermal ageing between 80°C and 110°C, but extrapolation to the operating temperature (60°C) is not representative of the experimental data. The physical state (solid or molten) of the samples during thermal ageing does not explain the non-representativeness of accelerated ageing. The variations of mechanical properties can be linked to the evolution of the microstructure of each polymer and of their macromolecular architecture during thermo-oxidative ageing. Nevertheless, it is difficult to correlate the evolution of the chemical structure during ageing with the evolution of the mechanical properties. This study emphasizes the importance of the multi-scale analysis in order to have a comprehensive understanding of the ageing phenomena.

Des revêtements multicouche anticorrosion, ou peintures anticorrosion, sont utilisés dans de nombreuses applications industrielles telles que la protection d’emballages métalliques utilisés pour le transport ou l’entreposage de matériaux radioactifs. En conditions d’usage, les propriétés fonctionnelles de ces peintures peuvent être dégradées sous l’effet de la température et des conditions environnementales (lumière, dioxygène, humidité, …). Ces évolutions ont été attribuées au vieillissement des différentes couches de peinture constituant le revêtement anticorrosion (vernis de structure acrylique-siloxane, sous couches de type résine époxydique à durcisseur amine). Afin de mener à bien cette étude, une approche dite « multi-échelle ascendante » a été développée. Cette méthodologie, initialement focalisée sur la modification des propriétés physico-chimiques des polymères vierges constituant chaque couche du revêtement (depuis l’évolution de la structure chimique et de l’architecture macromoléculaire, vers les propriétés fonctionnelles), est ensuite progressivement complexifiée par l’ajout d’additifs à la formulation des peintures (pigments, particules barrières à l’oxydation ou anticorrosion, …) avant que le revêtement multicouche complet ne soit analysé dans son ensemble. Ce travail de thèse vise à identifier et à corréler les modifications de la structure chimique et de l’architecture macromoléculaire des différentes couches de peinture responsables de la modification des propriétés fonctionnelles du revêtement anticorrosion. / Anti-corrosive multilayer coatings, or anti-corrosive paints, are used in several industrial applications such as metallic package protection used for transportation or storage of radioactive materials. In working conditions, functional properties of these paints could be degraded under the influence heat or environmental conditions (light, oxygen, moisture …). Such evolutions had been attributed to the aging of the different paint layers that constituted the anticorrosive coating (acrylic-siloxane topcoat, epoxy resin with amine hardener undercoats). In order to properly carry out this study, a « bottom-up multiscale approach » has been developed. This methodology, initially focused on the physico-chemical modifications of neat polymers that constituted each layer of the coating (from chemical structure and macromolecular architecture evolutions to functional properties), is then complexified by adding filers to the paint formulations (pigments, barrier or anti-corrosive particles …). The complete multilayer coating analyses are the last steps of that methodology. The aim of this thesis is to identify and correlate the evolution of anti-corrosive multilayer coating functional properties to the chemical and architectural modifications in each different layer.

<p>Polymers are subjected to physical and chemical changes during their processing, service life, and further recovery, and they may also interact with impurities that can alter their composition. These changes substantially modify the stabilisation mechanisms and mechanical properties of recycled polymers. Detailed knowledge about how the different stages of their life cycle affect the degree of degradation of polymeric materials is important when discussing their further waste recovery possibilities and the performance of recycled plastics. A dual-pronged experimental approach employing multiple processing and thermo-oxidation has been proposed to model the life cycle of recycled high-impact polystyrene (HIPS). Both reprocessing and thermo-oxidative degradation are responsible for coexistent physical and chemical effects (chain scission, crosslinking, apparition of oxidative moieties, polymeric chain rearrangements, and physical ageing) on the microstructure and morphology of polybutadiene (PB) and polystyrene (PS) phases; these effects ultimately influence the long-term stability, and the rheological and mechanical behaviour of HIPS. The PB phase has proved to be the initiation point of HIPS degradation throughout the life cycle. Thermo-oxidation seems to have more severe effects on HIPS properties; therefore, it can be concluded that previous service life may be the part of the life cycle with the greatest influence on the recycling possibilities and performance of HIPS recyclates in second-market applications. The results from the life cycle degradation simulation were compared with those obtained from real samples from a large-scale mechanical recycling plant. A combination of different analytical strategies (thermal analysis, vibrational spectroscopy, and chromatographic analysis) is necessary to obtain a detailed understanding of the quality of recycled HIPS as defined by three key properties: degree of mixing, degree of degradation, and presence of low molecular weight compounds.</p>

Les résines époxy/amine obtenues grâce au mélange d’un prépolymère époxy et d’un durcisseur amine, sont utilisées dans divers domaines d’applications : peinture, potting de composés électroniques... L’objectif de cette thèse est la prédiction de la durée de vie de trois résines : DGEBA ou DGEBU/cycloalipahtique diamine, DGEBA/aliphatique diamine, soumises à un vieillissement thermo-oxydant. Pour cela, une étude multi échelle de l’oxydation est réalisée à différentes conditions de température (de 110°C à 200°C) et de pression d’oxygène (0,2 bars et 50 bars). A l’échelle moléculaire, la spectroscopie IRTF a montré la formation d’amides et de carbonyles. A l’échelle macromoléculaire, les coupures de chaînes semblent prédominantes lorsque le durcisseur est une diamine cycloaliphatique. En revanche, lorsque le système contient des séquences méthylènes portées par des segments flexibles, elles peuvent induire un mécanisme de réticulation qui peut prédominer. Ces résultats gouvernent l’évolution des propriétés fonctionnelles : la fragilisation mécanique et la dégradation des propriétés diélectriques de DGEBA/cycloaliphatique diamine se produit pour des temps d’exposition inférieurs à ceux observés pour DGEBA/aliphatique diamine. L’extrapolation des durées de vie est réalisée grâce à une modélisation cinétique basée sur un schéma mécanistique de l’oxydation des trois résines. La résolution de ce schéma cinétique permet la modélisation de l’ensemble des résultats expérimentaux (concentration en produits d’oxydation, coupures de chaînes et réticulation) pour une oxydation homogène ou bien sur des échantillons épais présentant un gradient d’oxydation. Les contraintes mécaniques engendrées lors de l’oxydation d’un échantillon épais (3 mm) de DGEBA/cycloaliphatique diamine ont été simulées afin de prédire la fissuration spontanée. / Epoxy/amine resins are thermoset materials made of epoxy prepolymer and amine hardener. Those materials are used in several industrial applications, such as paint or to encapsulate electronics. The main goal of this work is to predict lifetime of three resins: DGEBA or DGEBU/cycloaliphatic diamine, DGEBA/aliphatic diamine, in thermo-oxidative environment. In order to achieve this, a multi scale study of the oxidation is done, at several temperatures (from 110°C to 200°C) and oxygen partial pressures (0,2 bars et 50 bars). At molecular scale, the formation of amides and carbonyls has been noticed. At macromolecular scale, chain scission has been observed in epoxy/cycloaliphatic diamine but in DGEBA/aliphatic diamine cross linking seems to be predominant. Those properties are directly related to functional properties: mechanical and dielectric break down appear later in DGEBA/aliphatic diamine than in epoxy/cycloaliphatic diamine. The extrapolation of life is possible thank to kinetic modelling, based on chemical mechanistic scheme. The resolution of this kinetic scheme allowed us to model all experimental data (concentration of oxidation products, chain scission and cross linking), either in homogenous oxidation and in thick samples (3 mm). Stresses induced by oxidation in a thick sample of DGEBA/cycloaliphatic diamine have been simulated thanks to Matlab ® and finite elements by Abaqus ®.

L’introduction des composites dans des pièces structurelles critiques pour les aéronefs représente une réelle rupture technologique et nécessite des études spécifiques afin de maîtriser leur comportement et leur durabilité. Ce travail a pour objectifs de caractériser et de comprendre les mécanismes de vieillissement de composites interlock 3D à fibres de carbone et à matrice polymère lorsqu’ils sont soumis à des cycles thermiques.Dans ce but, un essai de cyclage thermique (-55°C/120°C), dont l’environnement thermique et gazeux est totalement maitrisé, a été mis en place pour le vieillissement d’échantillons composites représentatifs du motif interlock élémentaire. L’analyse des mécanismes de dégradation induits a été réalisée grâce i/ à la mise au point d’une méthode de caractérisation quantitative 3D de l’évolution des microfissures au cours du cyclage, basée sur des observations par microtomographie RX et sur le développement d’une procédure de traitement d’images spécifique, ii/ au développement d’un essai de cyclage thermique in situ synchrotron couplé à une technique de corrélation d’images volumiques 3D, et iii/ à des simulations par éléments finis prenant en compte l’architecture réelle des échantillons à l’échelle mésoscopique et le comportement thermo-viscoélastique de la matrice.Les résultats obtenus mettent en évidence des couplages thermo-chimio-mécaniques complexes,qui s’expriment à travers quatre paramètres influents : le temps (et le nombre de cycles),l’architecture de l’interlock, la ténacité de la matrice et sa sensibilité à la thermo-oxydation. / The introduction of composite materials in critical structural parts for aircrafts represents a real technological breakthrough and requires specific studies to understand their behavior and durability. This work aims to characterize and understand the ageing mechanisms incarbon/epoxy 3D interlock composites when they are submitted to thermal cycling.For this purpose, a thermal cycle test (-55°C/120°C), whose heat and gaseous environment istotally mastered, was set up for the ageing of composite samples of elemental interlock pattern dimensions. Analysis of induced degradation mechanisms was achieved by i/ the development ofa 3D quantitative characterization method of the evolution of microcracks during cycling, basedon observations by microtomography RX and the development of a specific image processing procedure, ii/ the development of an in situ thermal cycle test under synchrotron light, coupled to a digital volume correlation technique, and iii/finite elements simulations taking into account the actual mesoscopic architecture of the samples and the thermo-viscoelastic behavior of thematrix.The results reveal complex thermo-chemo-mechanical couplings that are linked to four important parameters: time (and the number of cycles), the interlock architecture, the matrix toughness andits sensitivity to thermo-oxidation.

Polymers are subjected to physical and chemical changes during their processing, service life, and further recovery, and they may also interact with impurities that can alter their composition. These changes substantially modify the stabilisation mechanisms and mechanical properties of recycled polymers. The assessment of the quality properties of recycled polymers is therefore crucial to guarantee the performance of recyclates in further applications. Three key quality properties have been defined for this quality analysis: degree of mixing (composition), degree of degradation, and presence of low molecular weight compounds (degradation products, contaminants, additives). Furthermore, detailed knowledge about how the different stages of their life cycle affect the degree of degradation of polymeric materials is important when discussing their further waste recovery possibilities and the performance of recycled plastics. A dual-pronged experimental approach employing multiple processing and thermo-oxidation has been proposed to model the life cycle of recycled high-impact polystyrene (HIPS used in packaging applications, and electrical and electronic equipment (E&E). Both reprocessing and thermo-oxidative degradation are responsible for coexistent physical and chemical effects (chain scission, crosslinking, apparition of oxidative moieties, polymeric chain rearrangements, and physical ageing) on the microstructure and morphology of polybutadiene (PB) and polystyrene (PS) phases; these effects ultimately influence the long-term stability, and the rheological and mechanical behaviour of HIPS. The PB phase has proved to be the initiation point of HIPS degradation throughout the life cycle. Thermo-oxidation seems to have more severe effects on HIPS properties; therefore, it can be concluded that previous service life may be the part of the life cycle with the greatest influence on the recycling possibilities and performance of HIPS recyclates in second-market applicat / Vilaplana Domingo, FJ. (2008). Analytical strategies for the quality assessment of recycled high-impact polystyrene (HIPS) [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/2186 / Palancia