Inscrite dans le cadre d’un projet ANR, la thèse porte sur l’étude et le développement des revêtements poudres UV en vue du recouvrement de panneaux de bois. La thèse détaille les spécificités de ces formulations et de la technologie associée afin de constituer une bibliographie solide propre à ce domaine. Les travaux expérimentaux se basent sur des formulations modèles comprenant une résine poudre UV (uréthane diacrylate ou polyester diméthacrylate) et un photoamorceur. Une étude mécanistique permet de montrer les influences de la température et de la viscosité, de l’intensité lumineuse et de l’atmosphère sur la réactivité des formulations modèles. Il est également démontré que les mécanismes de terminaison spécifiques à ces systèmes suivent des processus mixtes: bimoléculaire, pseudo-monomoléculaire et recombinaison des radicaux primaires. La prédominance des différents processus dépend de l’avancement de la réaction. La formation du réseau de réticulation est ensuite étudiée en fonction de la source d’irradiation: convoyeur semi-industriel doté de lampes UV ou système LED émettant autour de 395 nm. Les caractéristiques du réseau de réticulation (Tg, densité de réticulation, module d’Young) sont reliées aux propriétés des revêtements finaux (flexibilité, résistance à la rayure ou au solvant). L’utilisation d’acrylates multifonctionnels a un impact sur les longueurs de chaînes et la densité de réticulation. En vue d’applications spécifiques, il est finalement proposé d’incorporer une argile modifiée avec de l’Argent au sein des formulations modèles pour obtenir des revêtements poudres UV antibactériens homogènes possédant de bonnes propriétés de résistance. / In the frame of a project of the Agency National Research (France), the thesis deals with the study and the development of UV powder coatings dedicated to wood based panels. The work describes the main features of these formulations and the associated technology in order to offer a strong bibliography specific to this area. The experiments are based on model formulations containing an UV powder resin (diacrylate urethane or dimethacrylate polyester) and a photoinitiator. A mechanistic study allows highlighting the influence of temperature and viscosity, light intensity and atmosphere on the reactivity of the model formulations. It is also shown that the termination mechanisms specific to theses systems follow mixed processes: bimolecular, pseudo-monomolecular and primary radical termination. The predominance of the different processes is related to the reaction conversion. The building of the crosslinking network is then studied depending of the irradiation source: semi-industrial conveyor equipped with UV lamps or LED system emitting around 395 nm. The characteristics of the crosslinking network (Tg, crosslinking density, Young’s modulus) are linked to the final coatings properties (flexibility, scratch and solvent resistance). The incorporation of multifunctional acrylates affects the chains length and crosslinking density. To reach specific applications, it is finally proposed to add a silver-modified clay into model formulations to obtain homogeneous antibacterial UV powder coatings exhibiting good resistance properties.

Yttria-stabilized zirconia-based thermal barrier coating systems are the most widely used commercial coatings in the industry, with practical applications in aircraft engines and land-based power turbines. The purpose of thermal barriers is primarily to protect the substrate from high temperatures and also to increase its oxidation resistance. Currently, concerning the relatively frequent volcanic eruptions and increasing air traffic intensity in desert areas, increased attention is being paid to the development of new thermal and environmental coatings that will withstand the so-called CMAS attack and still successfully meeting the strictest requirements of the aerospace industry. Two newly developed experimental coatings consisting of three successive layers have been developed for this work. The upper two layers are thermal insulating ceramic coatings, where two different uppermost coatings were deposited. The first uppermost layer of the coating is a mixture of mullite and hexacelsian in a ratio of 70/30 wt. %. The second upper most type of coating consists of Al6Si2O13 + MgAl2O4 + BaCO3 in a ratio of 6:3:1 wt. %. The interlayer is made of the commercially utilized yttria-stabilized zirconia. The metallic CoNiCrAlY coating, which is directly deposited on the nickel-based superalloy MAR-M247, fulfils a compensatory function between the mechanical properties of the nickel superalloy and the ceramic coating. The thermal and environmental barrier system was deposited using air plasma spraying (APS) technology. The main objective of this work was to evaluate the effect of the newly developed thermal and environmental barrier coating, which has a high potential for the protection of component surfaces in an aggressive environment, on isothermical and thermomechanical fatigue behaviour of nickel-based superalloy MAR-M247. Low cycle fatigue tests were performed in strain control mode with constant strain amplitude on both uncoated and TEBC coated superalloy. Fatigue hardening/softening curves, cyclic stress-strain curves and fatigue life curves in the representation of total strain amplitude, plastic strain amplitude and stress amplitude on the number of cycles to failure were obtained. Microstructural analysis of MAR-M247 superalloy and a newly developed experimental coating was performed in a scanning electron microscope. The fatigue crack initiation sites were identified and the process of fatigue crack propagation was described. The dislocation arrangement after fatigue loading of MAR-M247 was investigated in a transmission electron microscope. The findings of isothermical and thermomechanical low cycle fatigue behaviour of uncoated and TEBC coated MAR-M247 superalloy and identification of damage mechanisms presented in this dissertation will improve the estimation of safe-life that is particularly relevant to aircraft engines components.

The recent emphasis on magnesium alloys can be appreciated by following the research push from several agencies, universities and editorial efforts. With a density equal to two-thirds of Al and one-thirds of steel, Mg provides the best opportunity for lightweighting of metallic components. However, one key bottleneck restricting its insertion into industrial applications is low strength values. In this respect, Mg-Y-Nd alloys have been promising due to their ability to form strengthening precipitates on the prismatic plane. However, if the strength is compared to Al alloys, these alloys are not attractive. The primary reason for low structural performance in Mg is related to low alloying and microstructural efficiency. In this dissertation, these terminologies are discussed in detail. A simple calculation showed that the microstructural efficiency in Mg-4Y-3Nd alloy is 30% of its maximum potential. Guided by the definitions of alloying and microstructural efficiency, the two prime objectives of this thesis were to: (i) to use thermomechanical processing routes to tailor the microstructure and achieve high strength in an Mg-4Y-3Nd alloy, and (ii) optimize the alloy chemistry of the Mg-rare earth alloy and design a novel rare—earth free Mg alloy by Calphad approach to achieve a strength of 500 MPa. Experimental, theoretical and computational approaches have been used to establish the process-structure-property relationships in an Mg-4Y-3Nd alloy. For example, increase in strength was observed after post aging of the friction stir processed/additive manufactured microstructure. This was attributed to the dissolution of Mg2Y particles which increased the alloying and microstructural efficiency. Further quantification by numerical modeling showed that the effective diffusivity during friction stir processing and friction stir welding is 60 times faster than in the absence of concurrent deformation leading to the dissolution of thermally stable particles. In addition, the investigation on the interaction between dislocations and strengthening precipitate revealed that, specific defects like the I1 fault aid in the accelerated precipitation of the strengthening precipitate in an Mg-4Y-3Nd alloy. Also, the effect of external field (ultrasonic waves) was studied in detail and showed accelerated age hardening response in Mg-4Y-3Nd alloy by a factor of 24. As the bottleneck of low strength is addressed, the answers to the following questions are discussed in this dissertation: What are the fundamental micro-mechanisms governing second phase evolution in an Mg-4Y-3Nd alloy? What is the mechanical response of different microstructural states obtained by hot rolling, friction stir processing and friction stir additive manufacturing? Is defect engineering critical to achieve high strength Mg alloys? Can application of an external field influence the age hardening response in an Mg-4Y-3Nd alloy? Can a combination of innovative processing for tailoring microstructures and computational alloy design lead to new and effective paths for application of magnesium alloys?

Le sujet de cette thèse concerne les applications hautes températures, où les moteurs doivent être capables de fonctionner à 400°C pendant 2 heures, selon la norme en vigueur. Il convient dans ce type d’applications de disposer de matériaux assez stables pour que leurs propriétés isolantes restent inchangées, ce qui est le cas du fil émaillé PolyImide (PI). Ce fil émaillé pose néanmoins des problèmes économiques et de fournisseurs, d’où la nécessité de trouver d’autres alternatives. Ce travail de thèse a eu pour but de mettre au point et valider des techniques d’analyses (ATG / ATM / ATR-FTIR / DRS) adaptées au fil émaillé, et ce jusqu’à 400°C. Le PEI présente des propriétés insuffisantes pour ce type d’application car il se dégrade avant 350°C et perd ses propriétés d’isolation électrique. Le PAI est un matériau qui ne se dégrade que peu avant 400°C, et présente des caractéristiques électriques (propriétés diélectriques et de conduction) déjà plus proche du PolyImide. Nous avons pu établir la comparaison de deux PAI dont l’un est conventionnel et l’autre est un nanocomposite à base d’alumine. Ce dernier PAI est plus stable en température mais ne semble pas avoir de propriétés électriques très supérieures. Pour confronter les résultats expérimentaux obtenus dans des conditions particulières aux conditions réelles d’utilisation, des moteurs avec ces fils émaillés ont été fabriqués. Les moteurs équipés des fils PEI/PAI (fil standard) et PAI sont défaillants après 40 minutes au lieu de 2h, contrairement aux moteurs équipés de fil PI. La dégradation du PEI et le fluage du PAI, caractérisé au-delà de sa Tg (280°C), peuvent être la cause des dysfonctionnements de ces moteurs / This work is related to the high temperature application where motors have to withstand severe conditions - 400°C during 2 hours - according to the standard. Electrical insulation becomes a serious challenge for such application where materials have to remain stable, which is the case of PolyImide enameled wire. Other alternatives have to be found because this is a very expensive material with a small number of suppliers. The thermal, structural, mechanical and electrical properties of these systems have been investigated in-situ until 400°C by thermogravimetric analysis, ATR-FTIR microscopy, thermomechanical analysis, dielectric spectroscopy and DC voltage experiments. Dielectric spectroscopy has indicated a loss of insulating properties during the thermal cycle especially for PEI-containing enamels that degrades before 350°C. PAI enameled wires degrade just before 400°C, and electrical properties (dielectric properties and conductivity) are closer to PI‘s in this temperature range. A comparison between a conventional PAI and a PAI filled with nanoparticules of aluminium oxide has been made. The nanocomposite is thermally more stable but does not show better electrical behavior. To correlate all these results to the real test conditions (combined thermal, electrical and mechanical stresses), electrical motors have been fabricated using the enameled wires said before. They all breakdown after 40 minutes running, except motors made with PI enameled wires. The degradation of PEI ad the creeping of PAI up to its Tg (280°C) can explain the breakdown of these motors

Lors de cette étude, il a été étudié l'influence de l'ajout de microparticules de polymère réticulé (CPM) dans des formulations d'époxy-amine, sur la cinétique, la morphologie et les propriétés thermo-mécaniques des réseaux finaux obtenus. Tout d'abord, un protocole simple, robuste et bien contrôlé a été développé afin d’ obtenir une large gamme de taille de CPM, de Tg et de fonctionnalité amine. Ce protocole de polymérisation par précipitation, basé sur les phénomènes de séparation de phases, a également été appliqué à différentes compositions chimiques et différents monomères époxy hydrosolubles, ceci montrant les grandes possibilités de cette méthode. Une bonne interface entre les CPMs et la matrice a été recherchée en synthétisant les CPMs en excès de groupes amines. La quantification de ces groupes amines réactifs sur les CPMS était d'un grand intérêt et a donc été étudiée en profondeur. Le titrage des amines de surface a été réalisé en mettant au point un nouveau protocole qui a permis la quantification des amines primaires et secondaires sur les CPMs. Il a ensuite été mis en évidence que, bien que ces microparticules réticulées ne soient pas poreuses, des fonctions amines sont disponibles au cœur des particules et peuvent réagir avec d'autres molécules qui sont capables de diffuser dans la CPM. Il a été montré que lorsque les CPM ont été dispersées dans des mélanges d'époxy- amine, la diffusion des monomères dans le cœur de la CPM s'est produite mais différemment selon le procédé de dispersion. En effet, en utilisant le tétrahydrofurane comme solvant pour aider à la dispersion, la diffusion de la DGEBA est amplifiée et modifie les propriétés thermo-mécaniques du réseau final en modifiant le rapport stœchiométrique de la matrice. Le même phénomène a été observé mais moins amplifié lorsque les microparticules sont uniquement dispersées mécaniquement. En dispersant les CPMs dans l'amine qui est l'agent réticulant, on observe l'absorption complète de l'amine au coeur des CPMs, conduisant ainsi à la désorption de celle-ci dans une deuxième étape, permettant de créer le réseau. Ainsi, un comportement très complexe des CPM a été mis en évidence en présence des monomères et/ou solvant : le gonflement et les phénomènes de diffusion qui dépendent d'un certain nombre de paramètres tels que la température, la densité de réticulation des CPM, les paramètres de solubilité, etc. L'intensité du phénomène de diffusion conduit à une variété de comportements lorsque les CPMs sont ajoutées dans une formulation d'époxy-amine tels que: (a) une légère diminution du temps de gélification et l'augmentation de la conversion, (b) la modification de la température de transition vitreuse de la matrice. / Throughout this work, the influence of the addition of cross-linked polymer microparticles (CPMs) in epoxy-amine formulations on the kinetics, morphology and thermo-mechanical properties of the final networks have been investigated. First, an easy, robust and well-controlled protocol was developed to obtain a large range of CPM size, Tg and amine functionality. This protocol based on reaction induced phase separation via precipitation polymerization was also applied to different chemistries and water soluble epoxy pre-polymers showing the large possibilities of this method. The capacity of obtaining a good compatibility between the CPMs and the matrix was ensure by synthesizing the CPMs in excess of amino groups. The study of the remaining reactive amino groups on the CPMS was of great interest and therefore deeply investigated. The titration of the surface amine was performed by developing a new protocol that enabled the quantification of primary and secondary amines on CPMs. It was then highlighted that even though these cross-linked microparticles were not porous, amino groups are available into the core and can react with other molecules that are able to diffuse into the CPM core. It was shown that when CPMs were dispersed into epoxy-amine blends, the diffusion of monomers into the CPM core occurred but differently depending on the dispersion process. Indeed, using tetrahydrofuran as solvent to help for the dispersion increased the diffusion of DGEBA into the CPM core and changed the thermo-mechanical properties of the final network by modifying the stoichiometric ratio of the matrix. Same phenomenon was observed but less amplified when CPMs were mechanically dispersed in DGEBA. Regarding the dispersion of CPMs in the amine cross-linker, IPD, its complete absorption could be observed into the CPMs, leading then to the desorption of IPD to create the network. Thus, a very complex behavior of CPMs was highlighted in presence of monomers or/and solvent: swelling and diffusion phenomena that are dependent on a number of parameters such as temperature, CPM cross-link density, solubility parameters, etc. The intensity of those phenomena leads to a variety of behaviors when CPMs are added into an epoxy-amine formulation: (a) slight decrease of gel times and increase of conversion, (b) modification of glass transition temperature of the matrix.

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<p>Structural metallic materials exposed to energetic particle bombardments often experience various types of irradiation-induced microstructural damage, thus degrading the mechanical properties of the materials in form of irradiation hardening and embrittlement. Nanostructured materials have shown better radiation resistance than their coarse-grained (CG) counterparts due to the existence of abundant defect sinks, such as grain boundaries, twin boundaries, and phase boundaries. However, recently developed nanocrystalline (NC) steels show limited room-temperature tensile ductility (< 1%), which may become a concern for their future application for nuclear reactors. The focus of this thesis is to explore the strength-ductility dilemma in modified 9Cr1Mo (T91) ferritic/martensitic (F/M) steel processed by thermomechanical treatment (TMT) and surface severe plastic deformation (SSPD) with an attempt to fabricate strong, ductile and radiation resistant F/M steels. </p> <p><b>Carbon partitioning</b> between the quenched martensite and the other phases (bainitic ferrite or retained austenite) is critical for enhancing the strength and ductility of T91 steel. The tensile properties of partially tempered (PT) T91 steel can be tailored through introducing bainitic ferrite with high-density nanoscale transition carbides and refined lath martensite. In addition, retained austenite was introduced by increasing the carbon concentration of T91 steel to 0.6 wt.%. The carbon-modified steel processed by quenching partitioning (Q-P) treatment exhibits an ultrahigh strength, ~ 2 GPa, with a uniform strain of ~ 5% due to the existence of coherent carbides, ultrafine martensite and retained austenite. </p> <p>Meanwhile, surface mechanical grinding treatment (SMGT) on T91 steel reveals that introducing <b>gradient structures</b> on the sample surface contributes to a higher strength and an improved plasticity than its homogeneously structured counterpart. The deformation mechanism of the gradient structures was investigated with the assistance of quasi <i>in situ</i> crystal orientation analyses. Furthermore, <i>ex situ</i> He ion irradiation on the gradient T91 steel indicates that radiation-induced damage, such as bubble-induced swelling and irradiation hardening, were gradually mitigated by grain refinement from the sample surface to the center, resulting in superior radiation resistance. The results obtained from this thesis may facilitate the design and fabrication of strong, ductile and radiation-tolerant F/M steels.</p>

Utbredningen av en brand inuti en byggnad kan leda till global eller lokal strukturell kollaps, särskilt i stålramkonstruktioner. Faktum är att stålkonstruktioner är särskilt utsatta för termiska angrepp på grund av ett högt värde av stålkonduktivitet och tvärsnitten med små tjockleken. Som en viktig aspekt av konstruktionen bör brandsäkerhetskrav uppnås antingen enligt föreskrivande regler eller enligt antagande av prestationsbaserad brandteknik. Trots möjligheten att använda enkla metoder som involverar membersanalys kombinerat med nominella brandkurvor, är en mer exakt analys av det termomekaniska beteendet hos en stålkonstruktion ett tilltalande alternativ eftersom det kan leda till mer ekonomiska och effektiva lösningar genom att ta hänsyn till möjliga gynnsamma mekanismer. Denna analys kräver vanligtvis utredning av delar av strukturen eller till och med av hela strukturen. För detta ändamål och för att få en djupare kunskap om strukturelementens beteende vid förhöjd temperatur bör numerisk simulering användas. I denna avhandling utvecklades och användes termomekaniska finita element som är lämpliga för analys av stålkonstruktioner utsätta för brand. Relevanta fallstudier utfördes. Utvecklingen av både ett termomekaniskt skal- och 3D balkelement baserade på en korotationsformulering presenteras. De flesta relevanta strukturfall kan undersökas på ett adekvat sätt genom att antingen använda något av dessa element eller kombinera dem. Korotationsformuleringen är väl lämpad för analyser av strukturer där stora förskjutningar, men små töjningar förekommer, som i fallet med stålkonstruktioner i brand. Elementens huvuddrag beskrivs, liksom deras karakterisering i termomekaniskt sammanhang. I detta avseende övervägdes materialnedbrytningen på grund av temperaturökningen och den termiska expansionen av stål vid härledningen av elementen. Dessutom presenteras en grenväxlingsprocedur för att utföra preliminära instabilitetsanalyser och få viktig inblick i efterknäckningsbeteendet hos stålkonstruktioner som utsätts för brand. Tillämpningen av de utvecklade numeriska verktygen ges i den del av avhandlingen som ägnas åt det publicerade forskningsarbetet. Flera aspekter av knäckningen av stålkonstruktionselement vid förhöjd temperatur diskuteras. I Artikel I tillhandahålls överväganden om påverkan av geometriska imperfektioner på beteendet hos komprimerade stålplattor och kolonner vid förhöjda temperaturer, liksom implikationer och resultat av användningen av grenväxlingsprocedur. I Artikel II valideras det föreslagna 3D-balkelementet genom meningsfulla fallstudier där torsionsdeformationer är signifikanta. De utvecklade balk- och skalelementen används i en undersökning av knäckningsmotstånd hos komprimerade vinkel-, Tee- och korsformade stålprofiler vid förhöjd temperatur som presenteras i Artikel III. En förbättrad knäckningskurva för design presenteras i detta arbete. Som ett exempel på tillämpningen av principerna för brandsäkerhetsteknik presenteras en omfattande analys i Artikel IV. Två relevanta brandscenarier identifieras för den undersökta byggnaden, som modelleras och analyseras i programmet SAFIR. / The ignition and the propagation of a fire inside a building may lead to global or local structural collapse, especially in steel framed structures. Indeed, steel structures are particularly vulnerable to thermal attack because of a high value of steel conductivity and of the small thickness that characterise the cross-sections. As a crucial aspect of design, fire safety requirements should be achieved either following prescriptive rules or adopting performance-based fire engineering. Despite the possibility to employ simple methods that involve member analysis under nominal fire curves, a more accurate analysis of the thermomechanical behaviour of a steel structural system is an appealing alternative, as it may lead to more economical and efficient solutions by taking into account possible favourable mechanisms. This analysis typically requires the investigation of parts of the structure or even of the whole structure. For this purpose, and in order to gain a deeper knowledge about the behaviour of structural members at elevated temperature, numerical simulation should be employed. In this thesis, thermomechanical finite elements, suited for the analyses of steel structures in fire, were developed and exploited in numerical simulation of relevant case studies. The development of a shell and of a 3D beam thermomechanical finite element based on a corotational formulation is presented. Most of the relevant structural cases can be adequately investigated by either using one of these elements or combining them. The corotational formulation is well suited for the analyses of structures in which large displacements, but small strains occur, as in the case of steel structures in fire. The main features of the elements are described, as well as their characterization in the thermomechanical context. In this regard, the material degradation due to the temperature increase and the thermal expansion of steel were considered in the derivation of the elements. In addition, a branch-switching procedure to perform preliminary instability analyses and get important insight into the post-buckling behaviour of steel structures subjected to fire is presented. The application of the developed numerical tools is provided in the part of the thesis devoted to the published research work. Several aspects of the buckling of steel structural elements at elevated temperature are discussed. In paper I, considerations about the influence of geometrical imperfections on the behaviour of compressed steel plates and columns at elevated temperatures are provided, as well as implications and results of the employment of the branch-switching procedure. In Paper II, the proposed 3D beam element is validated for meaningful case studies, in which torsional deformations are significant. The developed beam and shell elements are employed in an investigation of buckling resistance of compressed angular, Tee and cruciform steel profiles at elevated temperature presented in Paper III. An improved buckling curve for design is presented in this work. Furthermore, as an example of the application of Fire Safety Engineering principles, a comprehensive analysis is proposed in Paper IV. Two relevant fire scenarios are identified for the investigated building, which is modelled and analysed in the software SAFIR.

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