Bisensitive interpenetrating polymer network (IPN) hydrogels of temperature sensitive net-poly(Nisopropylacrylamide) and pH sensitive net-poly(acrylic acid-co-acrylamide) for microfluidic applications were prepared via a sequential synthesis using free radical polymerization. The IPN indicated a suitable reversible alteration of swelling in response to the change in pH and temperature. The adequate change of the hydrogel volume is a basic requirement for microfluidic applications. Using the introduced correction factor f, it is possible to determine the cooperative diffusion coefficient (Dcoop) of cylindrical samples at any aspect ratio. The determined cooperative diffusion coefficient allowed the evaluation of varying swelling processes of different network structures. The presence of the second sub-network of the IPN improved the swelling behaviour of the first sub-network compared to the individual networks.

<p>When starch granules are gelatinized, many complex structural changes occur as a result of large quantity of water being absorbed. The enlargement of granule sizes and the leaching out water-soluble macromolecules contribute to the viscoelasticity. Starch pasting behavior greatly influences the texture of a variety of food products such as canned soup, sauces, baby foods, batter mixes etc. It is important to characterize the relationship between the structure, composition and architecture of the starch granules with its pasting behavior in order to arrive at a rational methodology to design modified starch of desirable digestion rate and texture. Five types of starch used in this study were waxy maize starch (WMS), normal maize starch (NMS), waxy rice starch (WRS), normal rice starch (NRS) and STMP cross linked normal maize starch. Evolution of volume fraction φ and pasting of 8% w/w starch suspension when heated at 60, 65, 70, 75, 80, 85 and 90 °C were characterized by particle size distribution and G’, G” in the frequency range of 0.01 to 10 Hz respectively. As expected, granule swelling was more pronounced at higher temperatures. At a fixed temperature, most of the swelling occurred within the first 5 min of heating. The pastes exhibited elastic behavior with G’ being much greater than G”. G’ increased with time for waxy maize and rice starch at all times. G’ and G’’ were found to correlated only to the temperature of pasting and not change much with the rate of heating. For WMS, WRS and STMP crosslinked NMS, G’ approached a limiting value for long heating times (30 min and above) especially at heating temperatures of 85°C and above. This behavior is believed to be due to the predominant effect of swelling at small times. For normal maize and rice starch, however, G’ reached a maximum and decreased at longer times for temperatures above 80 °C due to softening of granules as evidenced by peak force measurements. For each starch sample, the experimental data of G’ at different heating temperatures and times could be collapsed into a single curve. The limiting value of G’ at high volume fraction was related to granule size and granule interfacial energy using a foam rheology model. The interfacial free energy of granules were obtained from contact angle measurements and was employed to evaluate the limiting G’. The experimental data of G’ for all starches when subjected to different heating temperatures and times were normalized with respect to the limiting value at high volume fractions. The master curve for normalized G’ was employed to predict the evolution of G’ with time for different starches which was found to agree well with experimental data of storage modulus. A mechanistic model for starch swelling that is based on Flory Huggins polymer swelling theory was employed to predict the evolution of volume fraction of swollen granules. The model accounts for the structure and composition of different types of starches through starch-solvent interaction as quantified by static light scattering, gelatinization temperature and enthalpy of gelatinization, porosity and its variation with swelling and crosslinking of starch molecules within the granule from equilibrium swelling. Consequently, one could predict the evolution of texture of these starch suspension from the knowledge of their swelling behavior. Expressing the limiting storage modulus of complete swelling (volume fraction approaching unity) of starch suspension in terms of foam rheology, we were able to normalize the storage modulus of different types of starches with respect to its limiting value which is found to fall into a master curve. This master curve when employed along with the swelling model resulted in the successful prediction of development of texture for different types of starches. The above methodology can quantify the effects of structure and composition of starch on its pasting behavior and would therefore provide a rational guideline for modification and processing of starch-based material to obtain desirable texture and rheological properties.</p> <p> </p>

In this work, a design platform for the modeling, simulation and optimization of fluidic components and their interactions in larger systems is developed. A hydrogel-based stimulus-sensitive microvalve is the core element of the microfluidic toolbox. Essential material properties as swelling-stimuli functions and the cooperative diffusion are extracted from measurements. The results provide necessary input data for finite element simulations in order to extract characteristic properties of the mechanical and fluid domains. Finally, the behavior of the microvalve and other fluidic library elements is implemented in Matlab Simscape for component and system simulations. Case studies and design optimization can be realized in a very short time with high accuracy. The toolbox is suitable for research and development and as software for academic education. The library elements are evaluated for a chemofluidic NAND gate, a chemofluidic decoder and a chemofluidic oscillator.:1 Introduction to Microfluidic Systems 1.1 Chemofluidic Enables Scalable and Logical Microfluidics 1.2 Focus of this Work 2 Fundamentals for Hydrogel-based Lab-on-Chip Systems 2.1 Basic Hydrogel Material Behavior 2.1.1 Basic Swelling Behavior 2.1.2 General Properties of Hydrogels 2.2 Overview of the used Microtechnology 2.2.1 Synthesis of P(NIPAAm-co-SA) 2.2.2 Microfabrication of a Microfluidic Chip 2.3 Introduction to Modeling and Simulation Techniques 2.3.1 Computer-aided Design Methodologies 2.3.2 Model Abstraction Levels for Computer-Aided Design 2.3.3 Modeling Techniques for Microvalves in a Fluidic System 3 Analytical Descriptions of Swelling 3.1 Quasi-Static Description 3.1.1 Physical Static Chemo-Thermal Description 3.1.2 Finite Element Routine for Static Thermo-Elastic Expansion 3.1.3 Static System Level Design for Hydrogel Swelling 3.2 Transient Description 3.2.1 Physical Dynamic Chemo-Thermal Description 3.2.2 Finite Element Routine for Dynamic Thermo-Elastic Expansion 3.2.3 Transient System Level Design for Hydrogel Swelling 3.3 Swelling Hysteresis Effect 3.3.1 Quasi-static Hysteresis 3.3.2 Transient Hysteresis 4 Characterization of Hydrogel 4.1 Data Acquisition through Automated Measurements 4.1.1 Measuring the Swelling of Hydrogels 4.1.2 Contactless Measurement Concept to Determine the Core Stiffness of Hydrogels 4.2 Data Evaluation with Image Recognition 4.3 Data Fitting and Model Adaption 4.3.1 Quasi-static Response 4.3.2 Transient Response 4.3.3 Hysteresis Response 5 Modeling Swelling in Finite Elements 5.1 Validity of the Model and Simulation Approach 5.2 Thermo-Mechanical Model of the Hydrogel Expansion Behavior 5.2.1 Change of the Length by Thermal Expansion 5.2.2 Stress-Strain Relationship for Hydrogels 5.2.3 Thermal Volume Expansion and Parameter Adaptation 5.2.4 Heat Transfer Coefficient 5.3 Volume Phase-Transition of a Hydrogel implemented in ANSYS 5.4 Computational Fluid Dynamics 5.4.1 Analytic Mesh Morphing 5.4.2 One-way Fluid Structure Interaction Modeling 5.4.3 Towards a Two-way Fluid Structure Interaction Model in CFX 6 Lumped Modeling 6.1 The Chemical Volume Phase-transition Transistor Model 6.1.1 Static Hysteresis 6.1.2 Equilibrium Swelling Length – Quasi-static Behavior 6.1.3 Kinematic Swelling Length - Transient Behavior 6.1.4 Stiffness and Maximum Closing Pressure 6.1.5 Calculation of the Fluidic Conductance 6.1.6 Modeling of the Fluid Flow through the Valve 6.2 Circuit Descriptions Analogy for Microfluidic Applications 6.2.1 Advantages and Limitations of Combined Simulink-Simscape Models 6.2.2 Requirements for Microfluidic Circuits 6.2.3 Graphical User Interfaces and Library Element Management 6.3 Modeling Techniques for the Chemical Volume Phase-transition Transistor (CVPT) 6.3.1 Network Description of CVPT 6.3.2 Signal Flow Description of CVPT 6.3.3 Mixed Signal Flow and Network Model for CVPT 7 Micro-Fluidic Toolbox 7.1 Microfluidic Components 7.1.1 Fluid Sources and Stimuli Sources 7.1.2 Fluidic Resistor with Bidirectional Stimulus Transport 7.1.3 Junctions 7.1.4 Chemical Volume Phase-transition Transistor 7.2 Microfluidic Matlab Toolbox 7.3 Modeling Chemofluidic Logic Circuits 7.3.1 Chemofluidic NAND Gate 7.3.2 Chemofluidic Decoder Application 7.3.3 Chemo-Fluidic Oscillator 7.4 Layout Synthesis 8 Summary and Outlook Appendix A 2D Thermo-Mechanical Solid Element for the Finite Element Method B Thermal Expansion Equation for ANSYS C Linear Regression of the Thermal Expansion Equation for ANSYS D Comparing different Mechanical Strain Definitions E Supporting Documents E.1 Analytic Static Swelling E.2 FEM - Matrix Method E.3 8 Node Finite Element Routine E.4 FEM - Script to create the CTEX table data E.5 Comparison of Solid Mechanics / In dieser Arbeit wird eine Entwurfsplattform für die Modellierung, Simulation und Optimierung von fluidischen Komponenten und deren Wechselwirkungen in größeren Systemen entwickelt. Ein Mikroventil auf der Basis von stimuli-sensitiven Hydrogelen ist das Kernelement des Entwurfstools. Wesentliche Materialeigenschaften wie das Quellverhalten und der kooperative Diffusionskoeffizient werden zu Beginn mit Messungen ermittelt. Mit Finite-Elemente-Simulationen werden aus diesen Daten charakteristische Kennwerte für das mechanische und fluidische Verhalten bestimmt. Sie bilden die Basis für komplexe Systemmodelle in Matlab Simscape, welche das Mikroventil und weitere fluidische Grundelemente in ihrem Zusammenwirken beschreiben. Verschiedene Konzepte können in kurzer Zeit und mit hoher Genauigkeit analysiert, optimiert und verglichen werden. Die Toolbox eignet sich für die Forschung und Entwicklung sowie als Software für die akademische Ausbildung. Sie wurde für den Entwurf eines chemofluidischen NAND-Gatters, für einen chemofluidischen Decoder und für einen chemofluidischen Oszillator eingesetzt.:1 Introduction to Microfluidic Systems 1.1 Chemofluidic Enables Scalable and Logical Microfluidics 1.2 Focus of this Work 2 Fundamentals for Hydrogel-based Lab-on-Chip Systems 2.1 Basic Hydrogel Material Behavior 2.1.1 Basic Swelling Behavior 2.1.2 General Properties of Hydrogels 2.2 Overview of the used Microtechnology 2.2.1 Synthesis of P(NIPAAm-co-SA) 2.2.2 Microfabrication of a Microfluidic Chip 2.3 Introduction to Modeling and Simulation Techniques 2.3.1 Computer-aided Design Methodologies 2.3.2 Model Abstraction Levels for Computer-Aided Design 2.3.3 Modeling Techniques for Microvalves in a Fluidic System 3 Analytical Descriptions of Swelling 3.1 Quasi-Static Description 3.1.1 Physical Static Chemo-Thermal Description 3.1.2 Finite Element Routine for Static Thermo-Elastic Expansion 3.1.3 Static System Level Design for Hydrogel Swelling 3.2 Transient Description 3.2.1 Physical Dynamic Chemo-Thermal Description 3.2.2 Finite Element Routine for Dynamic Thermo-Elastic Expansion 3.2.3 Transient System Level Design for Hydrogel Swelling 3.3 Swelling Hysteresis Effect 3.3.1 Quasi-static Hysteresis 3.3.2 Transient Hysteresis 4 Characterization of Hydrogel 4.1 Data Acquisition through Automated Measurements 4.1.1 Measuring the Swelling of Hydrogels 4.1.2 Contactless Measurement Concept to Determine the Core Stiffness of Hydrogels 4.2 Data Evaluation with Image Recognition 4.3 Data Fitting and Model Adaption 4.3.1 Quasi-static Response 4.3.2 Transient Response 4.3.3 Hysteresis Response 5 Modeling Swelling in Finite Elements 5.1 Validity of the Model and Simulation Approach 5.2 Thermo-Mechanical Model of the Hydrogel Expansion Behavior 5.2.1 Change of the Length by Thermal Expansion 5.2.2 Stress-Strain Relationship for Hydrogels 5.2.3 Thermal Volume Expansion and Parameter Adaptation 5.2.4 Heat Transfer Coefficient 5.3 Volume Phase-Transition of a Hydrogel implemented in ANSYS 5.4 Computational Fluid Dynamics 5.4.1 Analytic Mesh Morphing 5.4.2 One-way Fluid Structure Interaction Modeling 5.4.3 Towards a Two-way Fluid Structure Interaction Model in CFX 6 Lumped Modeling 6.1 The Chemical Volume Phase-transition Transistor Model 6.1.1 Static Hysteresis 6.1.2 Equilibrium Swelling Length – Quasi-static Behavior 6.1.3 Kinematic Swelling Length - Transient Behavior 6.1.4 Stiffness and Maximum Closing Pressure 6.1.5 Calculation of the Fluidic Conductance 6.1.6 Modeling of the Fluid Flow through the Valve 6.2 Circuit Descriptions Analogy for Microfluidic Applications 6.2.1 Advantages and Limitations of Combined Simulink-Simscape Models 6.2.2 Requirements for Microfluidic Circuits 6.2.3 Graphical User Interfaces and Library Element Management 6.3 Modeling Techniques for the Chemical Volume Phase-transition Transistor (CVPT) 6.3.1 Network Description of CVPT 6.3.2 Signal Flow Description of CVPT 6.3.3 Mixed Signal Flow and Network Model for CVPT 7 Micro-Fluidic Toolbox 7.1 Microfluidic Components 7.1.1 Fluid Sources and Stimuli Sources 7.1.2 Fluidic Resistor with Bidirectional Stimulus Transport 7.1.3 Junctions 7.1.4 Chemical Volume Phase-transition Transistor 7.2 Microfluidic Matlab Toolbox 7.3 Modeling Chemofluidic Logic Circuits 7.3.1 Chemofluidic NAND Gate 7.3.2 Chemofluidic Decoder Application 7.3.3 Chemo-Fluidic Oscillator 7.4 Layout Synthesis 8 Summary and Outlook Appendix A 2D Thermo-Mechanical Solid Element for the Finite Element Method B Thermal Expansion Equation for ANSYS C Linear Regression of the Thermal Expansion Equation for ANSYS D Comparing different Mechanical Strain Definitions E Supporting Documents E.1 Analytic Static Swelling E.2 FEM - Matrix Method E.3 8 Node Finite Element Routine E.4 FEM - Script to create the CTEX table data E.5 Comparison of Solid Mechanics

Ionic hydrogels belong to the class of polyelectrolyte gels or ionic gels. Their ability to swell or shrink under different environmental conditions such as change of pH, ion concentration or temperature make them promising materials, e.g. for microsensoric or microactuatoric devices. The hydrogel swelling exhibits nonlinear effects due to the occurrence of different interacting transport phenomena. Numerical simulations are an essential part in the ongoing development of microsensors and microactuators. In order to determine transport effects due to diffusion, migration and convection a multiphase mesoscale model based on the Theory of Porous Media is applied. The governing field equations are solved in the transient regime by applying the Finite Element Method. By means of the derived numerical framework a detailed investigation of the different transport phenomena is carried out. Numerical experiments are performed to characterize the dominating transfer phenomena for ionic gels under chemical stimulation.

We propose a moving-boundary scenario to model the penetration of diffusants into rubbers. Immobilizing the moving boundary by using the well-known Landau transformation transforms the original governing equations into new equations posed in a fixed domain. We solve the transformed equations by the finite element method and investigate the parameter space by exploring the eventual effects of the choice of parameters on the overall diffusants penetration process. Numerical simulation results show that the computed penetration depths of the diffusant concentration are within the range of experimental measurements. We discuss numerical estimations of the expected large-time behavior of the penetration fronts. To have trust in the obtained simulation results, we perform the numerical analysis for our setting. Initially, we study semi-discrete finite element approximations of the corresponding weak solutions. We prove both a priori and a posteriori error estimates for the mass concentration of the diffusants, and respectively, for the a priori unknown position of the moving boundary. Finally, we present a fully discrete scheme for the numerical approximation of model equations. Our scheme is based on the Galerkin finite element method for the space discretization combined with the backward Euler method for time discretization. In addition to proving the existence and uniqueness of a solution to the fully discrete problem, we also derive a priori error estimates for the mass concentration of the diffusants, and respectively, for the position of the moving boundary that fit to our implementation in Python. Our numerical illustrations verify the obtained theoretical order of convergence in physical parameter regimes.

Recycled concrete is among the rising eco-friendly construction materials which helps to reduce waste and the need for new natural resources. However, such concrete may present previous deterioration due to, for instance, alkali-silica reaction (ASR), which is an ongoing distress mechanism that may keep being developed in the recycled material. This work aims to evaluate the potential of further distress and crack development (i.e. initiation and propagation) of AAR-affected RCA concrete in recycled mixtures displaying distinct past damage degrees and reactive aggregate types. Therefore, concrete specimens incorporating two highly reactive aggregates (Springhill coarse aggregate and Texas sand) were manufactured in the laboratory and stored in conditions enabling ASR development. The specimens were continuously monitored over time and once they reached marginal (0.05%) and very high (0.30%) expansion levels, they were crushed into RCA particles and re-used to fabricate RCA concrete. The RCA specimens were then placed in the same previous conditions and the “secondary” ASR-induced development monitored over time. Results show that the overall damage in ASR-affected RCA concrete is quite different from affected conventional concrete, especially with regards to the severely damaged RCA particles, where ASR is induced by a reactive coarse aggregate, as the RCA particle itself may present several levels of damage simultaneously caused by past/ongoing ASR and newly formed ASR. Moreover, the influence of the original damage extent in such RCA concrete was captured by the slightly damaged RCA mixture eventually reaching the same damage level as the severely damaged mixture. Furthermore, the original extent of deterioration influence the “secondary” induced expansion and damage of RCA concrete since the higher the original damage level, the higher the cracks numbers and lengths observed in the RCA concrete for the same expansion level whereas wider cracks are generated by RCA having previously been subjected to slight damage thus indicating the difference in the distress mechanism as a function of original extent of damage. In addition, it has been found that distress on RCA containing a reactive sand generates and propagates from the residual mortar (RM) into the new mortar (NM) as opposed to RCA containing a reactive coarse aggregate, being generated and propagated from the original coarse aggregate (i.e. original virgin aggregate – OVA) into the NM. Likewise, RCA containing a reactive sand caused longer and higher number of cracks for the same “secondary” induced expansion than the RCA made of reactive coarse aggregate. Finally, novel qualitative and descriptive models are proposed in this research to explain ASR-induced distress generation and propagation on RCA mixtures made of reactive fine and coarse aggregates.

Cette thèse fait partie des programmes de recherche sur le vieillissement des ouvrages de génie civil nucléaire lancés par l’IRSN (Institut de Radioprotection et de Sûreté nucléaire) dans le cadre du projet de prolongement de la durée d’exploitation des centrales nucléaires françaises. Le but étant de contribuer à la connaissance des mécanismes de vieillissement des matériaux constitutifs des ouvrages non-remplaçables d’une centrale nucléaire, tels que les enceintes de confinement. En effet, leur comportement représente un point important pour l’évaluation de la sûreté des installations nucléaires, car elles représentent la troisième et la dernière barrière de confinement contre le relâchement éventuel des produits radioactifs dans l'environnement.Parmi les phénomènes intervenants lors du vieillissement des ouvrages, le développement éventuel des pathologies, notamment les réactions de gonflements internes (RGI) qui sont susceptibles de dégrader le béton et conduire à l’apparition des fissurations dans les structures touchées. Ces réactions de gonflement internes (RGI) englobent la réaction sulfatique interne (RSI), la réaction alcali-granulat (RAG) et la concomitance de ces deux. Il s’agit de réactions endogènes, se produisant suite à l’interaction des composants initiaux du matériau. Ces interactions peuvent avoir lieu suite à l’utilisation de granulats réactifs en cas de RAG et/ou suite à un échauffement important au jeune âge en cas de RSI. Dans les ouvrages nucléaires, l’éventualité de ces phénomènes ne peut pas être écartée. En effet, ils comportent des éléments structuraux massifs en béton armé pour lesquels un échauffement important a pu se produire lors de la prise du béton et des granulats réactifs ont pu être utilisés pendant la confection. Ce risque doit donc être étudié d’autant plus que le prolongement de la durée d’exploitation des installations est envisagé.Cependant, la cinétique d’apparition des désordres suite au développement de ces réactions dans les ouvrages est en général lente allant jusqu’à quelques dizaines d’années, d’où le recourt à des essais accélérés. Cependant les solutions pratiquées dans les laboratoires de recherche, consiste à utiliser des protocoles d’essais accélérés mis au point sur des éprouvettes de faibles dimensions.Le travail de recherche réalisé dans le cadre de cette thèse comporte trois grandes axes : la mise au point d’un protocole expérimental visant à accélérer les réactions de gonflement interne du béton à l’échelle de structures massives, l’analyse multi-échelle des phénomènes et la mise au point d’une instrumentation innovante adaptée à cette problèmatique. Trois maquettes (de dimensions 2,4 x 1,4 x 1 m3) représentatives d’un ouvrage massif ont été réalisées dans des conditions maitrisées et optimisées afin de favoriser respectivement le développement de la réaction sulfatique interne (RSI), de la réaction alcali-granulat (RAG) et de la concomitance des deux pathologies, RAG et RSI. Ceci a permis d’étudier ces pathologies et de les caractériser à une telle échelle.L’effet d’échelle sur la cinétique de gonflement est mis en évidence grâce à une étude expérimentale multi-échelle permettant de comparer l’évolution des réactions dans les maquettes avec leur évolution dans des éprouvettes en béton reconstitué et des carottages.Une méthode d’instrumentation innovante par fibres optiques a été spécifiquement développée pour ces maquettes, permettant de suivre l’évolution des pathologies dans la masse et d’en déduire les champs de déformation dans plusieurs plans d’intérêt. Les mesures sont utilisées pour décrire finement les mécanismes évolutifs du gonflement et la dégradation des structures. Ces mesures sont aussi utilisées comme référence pour des simulations numériques ultérieures. / This thesis is part of a research program on the aging of nuclear infrastructures launched by the IRSN (Institute for Radiological Protection and Nuclear Safety) within the project aiming to extend the lifespan of the French nuclear power plants. The goal is to contribute to the knowledge of aging mechanisms touching the constituents of non-replaceable structures of a nuclear power plant, such as the containment building. Matter of fact, the behavior of such structures is an important point for the safety assessment of nuclear installations because they represent the third and last barrier against the dispersion of radioactive particles in the environment. Among the phenomena involved in aging mechanisms, internal swellings reactions (ISR) are pathologies that can degrade concrete by causing swelling, cracking and major disorders in the affected structures. Internal swelling reactions (ISW) include the delayed ettringite formation (DEF), the alkali-aggregate reaction (AAR) and the concomitance of the two. These pathologies are endogenous reactions, occurring as a result of the interaction between the initial components of the material. These interactions take place following the use of reactive aggregates in case of AAR and/or following a significant warm-up at the concrete’s early age in case of DEF. In nuclear facilities, the possibility of these phenomena cannot be ruled out. Matter of fact, they include massive reinforced concrete elements for which a significant heating could have occurred at the early age. Moreover, reactive aggregates may have been used during the construction phase. Therefore those risks ought to be studied especially if the extension of the lifespan of these installations is envisaged.However, the kinetics of these reactions are generally slow and it can take for up to a few decades for disorders to appear in the structure. Among the solutions used in research laboratories, one is to use accelerated test methods developed on small specimens.The research work carried out in this context includes three major axis: the development of an experimental protocol to accelerate internal swelling reactions of concrete on a massive structure scale, multi-scale analysis of the phenomena involved and the development of innovative instrumentation adapted to this problem. The purpose is to allow better observation and understanding of swelling reactions at such scale. Hence, three representative massive concrete mock-ups whose dimensions are 2,4 x 1,4 x 1 m3 were realized under controlled and optimized conditions for the development of delayed ettringite formation (DEF), alkali silica reaction (ASR) and the concomitant ASR-DEF case respectively.The scale effect on swelling kinetics is demonstrated by an experimental study comparing the evolution of swelling reaction in the massive samples with the evolution in reconstituted concrete laboratory specimens as well as coring specimens.An innovative instrumentation method using optical fibers is also developed thus allowing the monitoring of the pathologies in the massive structures and the tracking of the respective deformation fields in several two-dimensional plans of interest. The measurements are to finely describe and help in understanding the evolutionary mechanisms of structural degradation and can be used subsequently as a reference for numerical simulations.

La connaissance et la maîtrise de la perméation des fluides au travers des gaines polymères sont des problématiques de première importance pour optimiser la structure des conduites flexibles transportant des fluides pétroliers, mais aussi d'une façon générale dans le cas des transports de gaz. Une des préoccupations majeures vise à une meilleure compréhension du comportement de ces matériaux et vise à décrire les interactions polymère-gaz dans les flexibles, en particulier dans le cas de mélanges pétroliers agressifs et dangereux contenant de l'H2S. Grâce à l'utilisation d'équipements expérimentaux permettant notamment d'effectuer des essais de perméabilité avec des mélanges gazeux présentant de très faibles proportions d'H2S, nous avons étudié l'influence de la composition du gaz sur les propriétés barrière de deux grades de PVDF utilisés dans les flexibles : le Coflon XD et le Coflon XD déplastifié. Dans une gamme de pression modérée, des effets de pression des gaz purs (CH4 et CO2), puis des effets de couplage entre les gaz CH4, CO2 et H2S ont été mis en évidence sur la perméabilité, la diffusion et la solubilité. Des méthodes de simulation moléculaire de type Monte Carlo dans l'ensemble osmotique ont en outre été utilisées pour étudier la solubilité des gaz dans le PE, notamment pour des pressions très élevées. Les résultats confirment tout d'abord des observations expérimentales faites à pression modérée : les modes de sorption sont de type Henry pour le CH4 et le CO2 et de type Flory-Huggins pour l'H2S. Ils permettent également de mettre en évidence des effets de pression hydrostatique qui limitent à la fois la sorption de gaz, mais également le gonflement du PE dans le domaine des très fortes pressions (jusqu’à 2000 bar) et ce même en condition de mélanges de gaz. Les effets mis en évidence dans cette étude ont été modélisés via des lois en exponentielle de type Flory-Huggins pour la solubilité, Long pour la diffusion et une approche basée sur les travaux de Naito pour les effets de pression hydrostatique observés sur la solubilité / Polymer materials are used in numerous applications where the knowledge and the control of their transport properties are required. Concerning the flexible oil and gas pipes, the main function of polymer sheaths is to ensure the pipe leakproofness with respect to the external environment and also the conveyed fluids such as water, acid gases, crude oil. It is essential to have a deeper understanding of phenomena concerning the permeation of gases at very high pressures and temperatures through thermoplastic polymers, more especially in term of interactions between polymer chains and gases mixtures and particularly with hydrogen sulfide. Thanks to the utilisation of apparatus developed to study the permeability of polymers in presence of gas mixtures, in particular with small contents of hydrogen sulphide, we studied the influence of the gas mixture composition on the barrier properties of two kinds of PVDF used in applications such as sheath of flexible pipes. In a moderate pressure range, pressure effects of pure gases (CH4 and CO2), then coupling effects between the gases CH4, CO2 and H2S have been evidenced on the permeability, the diffusion and the solubility. Monte Carlo simulations in the osmotic ensemble have been performed. It allowed studying the solubility of gases in PE, in particular at high pressure. The results first confirm the experimental observations made at moderate pressure: sorption mode are Henry for CH4 and CO2 and Flory Huggins for H2S. It also allow to evidence effects of hydrostatic pressure which limit gas sorption and polymer swelling in the domain of very high pressure (up to 2000 bar), even in gas mixture condition. The effects evidenced in this study have been modelled via exponential laws. A simplified Flory Huggins type for the solubility, a Long type for the diffusion and an approach based on the works of Naito to take into account the hydrostatic pressure effects observed on the solubility

No description available.

[pt] Geralmente, o ambiente marinho é o ambiente natural mais agressivo para tubulações metálicas, promovendo corrosão, levando a falhas catastróficas. O método de reparo tradicional metálico soldado é um método de reparo inconveniente e custoso para a indústria. Compósitos poliméricos (FRP) são um material com potencial para reparo devido a sua alta razão resistência/peso e alta resistência à corrosão e degradação ambiental. Porém, os compósitos poliméricos também são suscetíveis a degradação severa quando expostos a condições ambientais agressivas, incluindo absorção de água, temperatura, UV e pressão. Para um melhor entendimento do mecanismo de degradação, amostras de compósito de matriz polimérica reforçado por fibras de vidro e resina epóxi pura foram fabricados e analisados em função do tempo e temperatura de envelhecimento em uma atmosfera salina. Além disso, um grupo de compósitos tiveram suas bordas cobertas com resina epóxi para similar práticas reais comuns no campo, denominado coated FRP. Uma resina epóxi DGEBA bicomponente e um tecido bidirecional de fibras de vidro foram usados como matriz e reforço, respectivamente. O tecido de fibra de vidro detém de uma razão de fibras longitudinais por transversais de 2:1. Os materiais foram sujeitos a envelhecimento de névoa salina em três câmaras à 35, 55 e 70 Celsius por aproximadamente 15171 horas. A concentração de sal na solução usada foi 5.0 por cento por massa. As amostras foram periodicamente retiradas das câmaras de envelhecimento para terem seus ganhos de massa mensurados pelo método gravitacional. Suas mudanças dimensionais também foram capturadas para avaliação do comportamento de inchamento dos materiais. Análises térmicas com DSC e DMTA foram feitas para avaliar o grau de cura dos materiais poliméricos e os efeitos da temperatura na pós-cura do material. Análises químicas com testes FTIR foram feitas para investigar a ocorrência de processos de pós-cura, hidrólise e termo-oxidação durante o envelhecimento. Amostras de compósito para testes destrutivos de flexão e resistência ao cisalhamento (ILSS) foram testados periodicamente para terem suas degradações monitoradas com o tempo. Testes de Excitação por Impulso (IET) e Colorímetro foram realizados como testes não-destrutivos (NDT) complementares. A primeira parte deste trabalho foca na avaliação do comportamento de absorção de umidade nos compósitos e resina epóxi pura. A relação entre a capacidade de absorção de umidade dos materiais, considerando a fração volumétrica de fibras, foi investigada. Além disso, modelos de absorção não-Fickianos também foram aplicados aos dados experimentais do FRP e resina epóxi para considerar desvios do modelo Fickiano padrão. Com isso, relaxações poliméricas e interações polímero-água, assim como mudanças na rede polimérica induzidas por umidade e temperatura, foram investigados. Uma modificação ao modelo não-Fickiano de Berens-Hopfenberg (BH) foi proposta para incluir os efeitos de pós-cura na absorção de umidade; tal modificação aplicada a pós-cura não foi encontrada na literatura. Na segunda parte deste trabalho, o comportamento de inchamento da resina epóxi pura e compósitos revestidos e não-revestidos foi avaliado e correlacionado com a absorção de umidade. A ortotropia do compósito ficou evidente, visto que o material apresentou maior capacidade de inchamento na direção da espessura. Um modelo do tipo Fickiano foi implementado ao inchamento na espessura com o intuito de investigar deformação de inchamento de saturação e a frente de inchamento. A terceira parte deste trabalho foca nos testes destrutivos e na avaliação dos efeitos hidrotérmicos na degradação do material. A temperatura se mostrou um fator acelerador para degradação de propriedade. Além disso, uma metodologia para estimar a curva de serviço de sistemas de reparo e extrapolá-la para temperaturas mais baixas foi elaborada. Metodologias de extrapolação de propriedades para exposição hidrotérmica de longa duração não foram encontradas na literature. Parâmetros como platô de retenção de propriedade e taxa de degradação foram estimados para temperatura ambiente. Curvas de Arrhenius também foram plotadas para avaliar o tempo requerido para alcançar os níveis de retenção em cada temperatura testada. Por fim, duas técnicas não-destrutivas foram utilizadas no FRP e resina epóxi pura como testes complementares como forma de validar os resultados encontrados em outras técnicas. A Técnica de Excitação por Impulso (IET) foi realizada para obter o módulo de Young e boa correlação foi obtida entre o teste IET e o ensaio destrutivo de flexão. Através dos testes colorimétricos, os efeitos de umidade e temperatura foram visíveis, já que a mudança de cor da resina foi mais forte para tempos longos e temperaturas mais altas. / [en] Generally, the marine environment is the most aggressive natural environment for metallic pipelines, promoting corrosion, leading to catastrophic failures. The traditional welded metallic repairs are high-cost and inconvenient repair methods for the industry. Polymeric composites (FRP) are a potential repair material due to their high resistance/weight ratio and high resistance to corrosion and environmental degradation. However, polymeric composites are also susceptible to severe degradation when exposed to harsh environment conditions, including water absorption, temperature, UV and pressure. To better understand the degradation mechanism, glass-fiber reinforced polymer matrix composite (GFRP) and neat epoxy samples were fabricated and analyzed as a function of aging time and temperature in a saline atmosphere. In addition, a group of composites had their exposed edges coated with epoxy resin to simulate common real-life practices in the field, namely coated FRP. A two-component DGEBA epoxy resin and a bidirectional glass-fiber woven fabric were used as matrix and reinforcement, respectively. The fiberglass fabric had a longitudinal to transverse fiber ratio of 2:1. The materials were subjected to salt spray aging in three chambers at 35, 55 and 70 Celsius for approximately 15171 hours. The salt concentration in the solution used was 5.0 per cent by weight. Samples were periodically removed from the chambers to have their mass gain measured by the gravitational method. Their dimensional changes were also measured to evaluate the swelling behavior of the materials. Thermal analyses with DSC and DMTA were performed to evaluate the curing degree of the polymeric materials tested and the effects of temperature on the material’s post-curing. Chemical analyses with FTIR tests were performed to investigate the occurrence of post-curing, hydrolysis and thermo-oxidation processes during aging. Composite samples for bending and interlaminar shear strength (ILSS) destructive tests were periodically tested to have their degradation monitored over time. Impulse Excitation Technique and colorimetry tests were also performed as complementary non-destructive tests (NDT). The first part of this work focuses on the assessment of the moisture absorption behavior of both composite and neat epoxy resin. The relationship between the moisture gain capacity of the materials, considering the fiber volume fraction, was investigated. Besides, non-Fickian absorption models were also applied to the experimental data of FRP and neat epoxy resin to account for deviations from the standard Fickian model. Then, polymeric relaxations and polymer-water interactions, as well as network changes induced by moisture and temperature, were investigated. A modification to the Berens-Hopfenberg (BH) non-Fickian model was proposed to account for post-curing effects on the moisture absorption; such modification applied for post-curing was not found in literature. In the second part of this work, the swelling behavior of neat epoxy resin, uncoated and coated composites was evaluated and correlated with moisture absorption. The orthotropy of the composite was evident, since this material showed greater swelling capacity in the thickness direction. A Fickian-like model was implemented to the thickness swelling to investigate swelling strain saturation and swelling front. The third part of this work focuses on the destructive tests and evaluation of the hygrothermal effects on the material degradation. Temperature proved to be an accelerating factor for property degradation. In addition, a methodology to estimate the service-life curve of the repair systems and extrapolate it to lower temperatures was elaborated. The methodology of property extrapolation for long-term hygrothermal exposure in salt spray environments could not be found in literature. Parameters like property retention plateau and degradation rate were estimated for room temperature (25°C). Arrhenius curves were also plotted to evaluate the time required to reach the properties’ retention levels for each temperature. Finally, two non-destructive techniques were performed on the uncoated FRP and on neat epoxy resin as complementary tests in order to validate the results found in other techniques. The Impulse Excitation Technique (IET) was performed to evaluate the Young modulus and good correlation was found between IET and destructive bending tests. From the colorimetry tests, the effects of moisture and temperature were visible, as the resin s color change was stronger at longer aging time and higher temperatures.