Ion-containing block copolymers blend ionic liquid properties with well-defined polymer architectures. This provides conductive materials with robust mechanical stability, efficient processability, and tunable macromolecular design. Conventional free radical polymerization and anion exchange achieved copolymers containing n-butyl acrylate and phosphonium ionic liquids. These compositions incorporated vinylbenzyl triphenyl phosphonium and vinylbenzyl tricyclohexyl phosphonium cations bearing chloride (Cl), or bis(trifluoromethane sulfonyl)imide (Tf2N) counteranions. Differential scanning calorimetry and dynamic mechanical analysis provided corresponding thermomechanical properties. Factors including cyclic substituents, counteranion type, as well as ionic concentration significantly influenced phosphonium cation association. 1, 1\'-(1, 4-Butanediyl)bis(imidazole) neutralized NexarTM sulfonated pentablock copolymers and produced novel electrostatically crosslinked membranes. Variable temperature FTIR and 1H NMR spectroscopy confirmed neutralization. Atomic force microscopy and small angle X-ray scattering studied polymer morphology and revealed electrostatic crosslinking characteristics. Tensile analysis, dynamic mechanical analysis, thermogravimetric analysis, and vapor sorption thermogravimetric analysis investigated polymer properties. The neutralized polymer demonstrated enhanced thermal stability, decreased water adsorption, and well-defined microphase separation. These findings highlight NexarTM sulfonated pentablock copolymers as reactive platforms for novel, bis-imidazolium crosslinked materials. 4-Vinylbenzyl piperidine is a novel styrenic compound that observably autopolymerizes. In situ FTIR spectroscopy monitored styrene and 4-vinylbenzyl piperidine thermal polymerizations. A pseudo-first-order kinetic treatment of the thermal polymerization data provided observed rate constants for both monomers. An Arrhenius analysis derived thermal activation energy values. 4-Vinylbenzyl piperidine exhibited activation energy 80 KJ/mol less than styrene. The monomer differs from styrene in its piperidinyl structure. Consequently, in situ FTIR spectroscopy also monitored styrene thermal polymerization with variable N-benzyl piperidine concentrations. Under these circumstances, styrene revealed activation energy 60 KJ/mol less than its respective bulk value. The similarities in chemical structure between styrene and 4-vinylbenzyl piperidine suggested thermally initiated polymerization occurred by the Mayo mechanism.  The unique substituent is proposed to offer additional cationic effects for enhancing polymerization rates. Living anionic polymerization of 4-vinylbenzyl piperidine achieved novel piperidinyl-containing polymers.  Homopolymer and copolymer architectures of this design offer structural integrity, and emphasize base stability.  Sequential anionic polymerization afforded a 10K g/mol poly(tert-butyl styrene-co-4-vinylbenzyl piperidine) diblock and a 50K poly(tert-butyl styrene-co-isoprene-co-4-vinylbenzyl piperidine) triblock. Alkylation studies involving a phosphonium bromide salt demonstrated the future avenues for piperidinium based polymer designs. These investigations introduce piperidinyl macromolecules as paradigms for a new class of ammonium based ionic materials. / Master of Science

Thermomechanically bonded spunbond nonwoven fabrics contain discrete bonds that are formed by melted and fused fibers. Through equi-biaxial tensile testing and simultaneous image capture, the mechanical response of individual bonds was studied through loading in the preferential fiber direction, the machine direction, and in the direction that is perpendicular, the cross direction, of the fabric web. Independent biaxial force and displacement data were collected and analyzed, and the maximum force and stiffness of the bonds in the machine and cross directions were found to be statistically different. After scaling the maximum force and stiffness by a relative basis weight parameter, a fiber orientation parameter, and the width of the bond itself, the peak force and stiffness in the machine and cross directions were found to no longer be statistically different. This indicates that basis weight, fiber orientation, and bond size dictate the biaxial mechanical behavior of the bonds. Furthermore, significant fiber debonding was observed in all the bonds tested, effectively suggesting bond disintegration into the individual component fibers during testing. Digital image correlation, using the captured images, was utilized to calculate local and average Eulerian strains of the bond during the initial stages of the test. The strain experienced by the bonds in the machine direction was always positive and increasing as the biaxial load increased. The strain in the cross direction, however, experienced increasing and decreasing strain. Local strain maps revealed the highly inhomogeneous strain response of the bonds under biaxial loading. / Master of Science

The synthesis and characterization of a variety of ammonium ionenes from water-soluble coatings to high-performance elastomers are discussed. Water-soluble random copolymer ionenes were synthesized using the Menshutkin reaction from 1,12-dibromododecane, N,N,Nâ ²,Nâ ²-tetramethyl-1,6-hexanediamine, and 1,12-bis(N,N-dimethylamino)dodecane. The absolute molecular weights were determined for the first time using a multiangle laser light scattering detector in aqueous size exclusion chromatography and the weight-average molecular weights of these ionenes were in the range of 17,000-20,000 g/mol. Charge density increased with increasing molar ratio of N,N,Nâ ²,Nâ ²-tetramethyl-1,6-hexanediamine and the glass transition temperature (Tg) increased from 69 °C to 90 °C as the charge density increased. Small angle x-ray scattering (SAXS) showed isotropic scattering patterns for these ionenes. A limited study on cytotoxicity of these ionenes showed no direct correlation between charge density and cell viability for human brain microvascular endothelial cell line. A series of low hard segment (HS) content, poly(propylene glycol) (PPG)-based ammonium ionenes were synthesized using a Menshutkin reaction from bromine end-capped PPG oligomers (prepared using acid-chloride reactions) and N,N,Nâ ²,Nâ ²-tetramethyl-1,6-hexanediamine. Matrix assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry, titration analyses, and ¹H NMR spectroscopy, confirmed the difunctionality of bromine end-capped PPG oligomers. Thermal analysis revealed Tg's of -60 °C, comparable to pure PPG, using differential scanning calorimetery (DSC), dynamic mechanical analysis (DMA) confirming microphase separation, and an onset of degradation (Td) at 240 °C. Synthesis of a series of random block copolymer ammonium ionenes with an aliphatic 1,12-dibromododecane as part of the hard segment (33 wt% HS) enhanced film formation and supported microphase separation property. The Td and Tg did not change compared to PPG-ionenes with lower HS content. DMA and tensile testing demonstrated the influence of soft segment (SS) molecular weight and hard segment (HS) content on the mechanical properties of segmented ammonium ionenes. DMA showed the onset of flow, ranging from 100-140 ºC for 1K and 2K g/mol PPG-based ionenes respectively. SAXS revealed a Bragg distance scaled with soft segment molecular weight and ranged from 6.6 to 23.4 nm for 1K to 4K g/mol PPG-based ionenes, respectively. An investigation of the salt-responsive solubility property of random block copolymer PPG-ionenes revealed a dependence on PPG molecular weight. The 1K g/mol PPG-based ionenes with a hydrophilic (HPL)/hydrophobic (HPB) value ranging from one to three showed solubility in both water and one wt% NaCl aqueous solutions. The 2K g/mol PPG-based ionenes containing HPL/HPB value of two to 15 showed cloudy dispersions in water and one wt% NaCl solutions. The 4K g/mol PPG-based ionenes possessed the salt-responsive character; 4K g/mol PPG-based ionenes with HPL/HPB values of one to 12 showed milky dispersions in water, suspended particles in one wt% NaCl solutions and film precipitation at a HPL/HPB molar ratio of 19. / Master of Science

We use the three-dimensional finite element code DYNA3D to analyze two problems: (a) the normal impact of a cylindrical monolithic or composite rod against a smooth flat rigid target, (commonly known as the Taylor impact test), and (b) the penetration of composite and monolithic steel cylindrical rods into reinforced concrete targets. The composite rod is made of either a steel or copper shell enclosing a ceramic. The ceramic and the steel are assumed to fail at a critical value of the effective plastic strain, whereas no failure is considered in the copper. The thermoviscoplastic response of steel and copper is modeled by the Johnson-Cook relation and the ceramic and concrete are assumed to be elastic-plastic. Values of material parameters in the constitutive relation for the reinforced concrete (RC) are derived by the rule of mixtures. Failure of a material is simulated by the element erosion technique for ceramic and steel, and element erosion along with stiffness reduction for the RC. The effect of the angle of obliquity of impact on the damage induced in the target is ascertained. For the solid cylindrical copper rod impacting a smooth flat rigid target, the time history of the deformed length and the axial variation of the final diameter are found to match well with the experimental findings. For the composite rod, the diameter of the deformed impacted surface, the shape and size of the mushroomed region and the volume fraction of the failed ceramic material strongly depend upon the impact speed, the shell wall thickness and the thickness of the solid copper rod at the front end. Some composite cylindrical rods impacting at normal incidence RC targets were found to buckle during the penetration process in the sense that their outer diameter at a cross-section close to the impacted end increased by at least 20%. For steel penetrators, the damage experienced increased as the nose shape got blunter and the angle of obliquity became larger whereas the damage induced to the target only increased with penetrator bluntness. / Master of Science

Shape memory alloy (SMA) materials such as nitinol have unique properties associated with the shape recovery effect and the material’s phase changes that have been used in a variety of actuator and sensing applications. By embedding SMA elements into host composite materials, control or modification of the SMA hybrid composite’s structural properties can be accomplished in-service, thereby increasing the hybrid composite’s structural functionality. Previous studies addressed increasing composite materials’ functionality by enabling in-service control of their dynamic response. Utilizing the SMA’s substantial recovery stress and capacity to dissipate strain energy to increase the hybrid composite’s static functionality is addressed herein. Specific applications for SMA hybrid composites include improving composite material’s impact damage resistance and composite cylinder stress and deflection control. In stress and deflection control of cylindrical structures, SMA actuators are placed within the composite cylinder to form an active compound cylinder. The active SMA elements can significantly reduce the internal pressure-induced radial dilation and creep so that under severe loading, piston to cylinder tolerances may be maintained. Similar to a conventional metallic compound cylinder, the active compound cylinder also reduces peak cylinder hoop stresses. Hybridizing composites with nitinol improves their impact resistance because of nitinol’s tremendous capacity to absorb impact strain energy through the stress-induced martensitic phase transformation. The amount of impact damage is reduced and the material’s resistance to impact perforation at various velocities is improved. The experimental response of nitinol hybrid composites and the associated mechanics are presented. The unique toughness and resistance to permanent deformation that is a result of the stress-induced martensitic phase transformation enables the nitinol to absorb on the order of 4 times the strain energy of high alloy steel and 16 times that of many graphite/epoxy composites. In most static applications where SMA elements are used for reinforcement, maintaining the integrity of the interface between the SMA elements and the host polymeric matrix composite material is critical to operation. The relationship between preparation of SMA elements for hybrid composite fabrication and interfacial bond strength is presented to address this issue. The mechanics of interfacial shear failure between SMA element and composite is also presented. / Ph. D.

This research establishes a physics-based life determination model for the second generation single crystal superalloy PWA 1484 experiencing out-of-phase thermomechanical fatigue (TMF). The life model was developed as a result of a combination of critical mechanical tests, dominant damage characterization and utilization of well-established literature. The resulting life model improves life prediction over currently employed methods and provides for extrapolation into yet unutilized operating regimes. Particularly, the proposed deformation model accounts for the materials' coupled fatigue-environment-microstructure response to TMF loading. Because the proposed model is be based upon the underlying deformation physics, the model is robust enough to be easily modified for other single crystal superalloys having similar microstructure. Future use of this model for turbine life estimation calculations would be based upon the actual deformation experienced by the turbine blade, thereby enabling turbine maintenance scheduling based upon on a "retirement for a cause" life management scheme rather than the currently employed "safe-life" calculations. This advancement has the ability to greatly reduce maintenance costs to the turbine end-user since turbine blades would be removed from service for practical and justifiable reasons. Additionally this work will enable a rethinking of the warranty period, thereby decreasing warranty related replacements. Finally, this research provides a more thorough understanding of the deformation mechanisms present in loading situations that combine fatigue-environment-microstructure effects.

L’objectif de ce travail est de proposer une méthodologie simple pour évaluer l’intégrité et la durée de vie d’échangeurs thermiques soudés. Une approche à deux échelles est proposée. Une description macroscopique avec la prise en compte de la structure de l’échangeur est menée pour permettre des calculs thermoélastiques par éléments finis. La réponse mécanique de l’échangeur pour deschargements thermiques, cycliques, simples est évaluée. Notamment, les zones de concentration decontraintes sont repérées. A partir cette étude, une étude micromécanique du comportement dumatériau composant l’échangeur est menée. Le matériau considéré est un acier 316L. Soncomportement élastoplastique est identifié avec un écrouissage isotrope et cinématique. La tenuemécanique pour des chargements en fatigue oligocyclique est évaluée à l’aide d’un dispositif deflexion 4 points alternée et un critère de Manson-Coffin est identifié. Ce critère est utilisé pour évaluerle nombre de cycle admissible par l’échangeur pour une amplitude de chargement donnée. Pour cela,la déformation plastique attendue dans l’échangeur est évaluée à partir d’une équivalence en énergieaux endroits où la contrainte se concentre. Les prédictions du modèle ont été comparées de manièresatisfaisante avec les résultats expérimentaux menés sur un échangeur test, pour la réponsethermoélastique que pour l’évaluation du nombre de cycles à rupture. / This study proposes a simple methodology to estimate the mechanical response and lifetime of weldedheat exchangers subjected to thermal loadings. The structure of the heat exchanger is modeled toestimate its mechanical response for thermal loads. Thermoelastic calculations are carried out with thefinite elements method. From these simulations, the regions where the stress concentrates areidentified. Then, a micromechanics approach is adopted to identify the material’s elastic plasticresponse with isotropic and kinematic hardening. Its durability under oligocyclic fatigue isinvestigated with an original 4 points alternate bending.d vice. From these experiments, a Manson-Coffin criterion is identified. This criterion is used to estimate the heat exchangers lifetime in terms ofmaximum cycles for thermal loadings with different magnitude. To this end, the plastic deformation isestimated from the macroscopic calculation with an energy equivalence between the thermoelasticcalculation and the non linear one. The predictions are found in agreement with experimental datacarried out on test-heat exchangers, for both the thermoelastic response and the number at cycles atrupture.

Une analyse du comportement thermomécanique du caoutchouc naturel est réalisée en combinant deux techniques d'imagerie quantitative. La corrélation d'images visibles sert à estimer les déformations puis l'énergie de déformation alors que des images infrarouges permettent d'estimer, via l'équation de diffusion, les quantités de chaleur mise en jeu. La construction de bilans d'énergie montre alors l'importance relative des mécanismes dissipatifs et de couplage thermomécanique. A basse fréquence pour de faibles déformations, les résultats permettent de retrouver le fameux effet d'inversion thermoélastique. A déformation plus importante, les résultats montrent une compétition sur le plan énergétique entre élasticité entropique et mécanismes de cristallisation/fusion sous contrainte. Aucun effet dissipatif significatif n'est détecté à basse comme en haute fréquence alors que dans chaque cas, sur le plan mécanique, une aire d'hystérésis caractérise la réponse cyclique du matériau. / An analysis of the thermomechanical behavior of the natural rubber is carried out by combining two quantitative imaging techniques. The digital image correlation of visible images is used to estimate the strain and then the deformation energy whereas infrared images make it possible to estimate, via the heat equation, the amounts of heat involved in the material transformation. The construction of energy balance enables us to determine the relative importance of the dissipative and thermomechanical coupling mechanisms. For low frequency and low extension ratio, the results show the famous thermoelastic inversion effect. From an energy standpoint, a competition between entropic elasticity and stress-induced crystallization/fusion mechanisms is observed for more significant extension ratios. No significant dissipative effect can be detected at low or high loading frequency whereas in each case, a stress-strain hysteresis characterizes the cyclic response of the material.

Les matériaux composites TRC (Textile Reinforced Concrete), consistant d'une matrice cimentaire et d'un renforcement par des textile ou fibres (en carbone, en verre ou en autre matière, …) sont souvent utilisés pour réparer ou/et renforcer les éléments structurels porteurs (dalle, poutre, colonne) d'anciens ouvrages de génie civil. Ils peuvent être également utilisés comme des éléments porteurs dans les structures neuves (éléments de préfabrications). Afin de développer des composites TRC avec de bonnes caractéristiques à température élevée, on a fait une combinaison entre les textiles de carbone qui possède une bonne capacité mécanique et une matrice réfractaire qui assurent une transmission de charge entre le textile de renforcement et les protège thermiquement contre l'action de température élevée. Le comportement thermomécanique des composites TRC de carbone est expérimentalement et numériquement étudié à l'échelle mésoscopique dans cette thèse. L'avancement scientifique sur ce sujet de thèse permettrait d'améliorer la stabilité au feu des structures qui sont renforcées par des matériaux composites TRC. Ce sujet contribuerait aux intérêts sociaux et économiques significatifs pour le génie civil dans le monde entier en général et au Vietnam en particulier. La thèse concerne la caractérisation expérimentale et modélisation numérique du comportement thermomécanique à température élevée des matériaux composites TRC à l'échelle mésoscopique. Dans une première partie expérimentale, les textiles de carbone (des produits commerciaux sur le marché), la matrice du béton réfractaire et l'interface textile/matrice ont été testés au régime thermomécanique à température constante (allant de 25 °C à 700 °C). Les résultats obtenus montrent un effet du traitement du textile sur le comportement et mode de rupture des textiles de carbone et de l'interface textile/matrice. Un modèle analytique a été également utilisé pour déterminer l'évolution des propriétés thermomécaniques des textiles de carbone en fonction de la température. Le transfert thermique dans l'éprouvette cylindrique du béton réfractaire a été réalisé pour valider les propriétés thermiques du béton réfractaire. Tous les résultats obtenus dans cette partie sont utilisés comme données pour le modèle numérique dans la partie de modélisation. La deuxième partie expérimentale explore le comportement thermomécanique des TRCs sous deux régimes : thermomécanique à température constante et thermomécanique à force constante. Deux textiles de carbone, qui ont donné les meilleures performances à température élevée, ont été choisis pour une fabrication des TRCs. Les résultats expérimentaux montrent un comportement thermomécanique avec l'écrouissage (trois ou deux phases) à température modérée et un comportement fragile à température supérieure de 500 °C. Au régime thermomécanique à force constante, deux composites TRCs peuvent résister plus long que les textiles de carbone seuls grâce à bonne isolation thermique de la matrice cimentaire. En comparant les deux résultats sur les éprouvettes de TRC, l'effet du renforcement de textile (le taux de renfort, le produit de traitement, la géométrie du textile) sur le comportement thermomécanique a été analysé. Tous les résultats expérimentaux de cette partie ont été utilisés pour valider et comparer avec ceux obtenus à partir du modèle numérique. La partie de modélisation numérique a deux buts : prédire le comportement thermomécanique global du composite TRC à partir des propriétés thermomécaniques des matériaux constitutifs ; valider le transfert thermique dans le composite en cas d'augmentation de la température pour prédire la température de rupture ou la durée d'exposition du composite [etc...] / TRC materials, consisting of a cement matrix and a reinforcement by textiles or fibers (carbon, glass or other fibre, etc) are often used to repair or/and strengthen the loading structural elements (slab, beam, column) of old civil engineering works. They can also be used as loading elements in new structures (prefabrication element). In order to develop TRC composites with good characteristics at high temperature, a combination has been made between the carbon textiles which have a good mechanical capacity and a refractory matrix which provides a load transfer between the reinforcement textiles and thermally protects them against the action of high temperature. The thermomechanical behavior of carbon TRC composites is experimentally and numerically studied at the mesoscale in this thesis. Scientific advancement on this thesis topic would improve the fire stability of structures that are reinforced by TRC composite materials. This topic would contribute to significant social and economic interests for civil engineering worldwide in general and Vietnam in particular. My thesis work concerns the experimental characterization and numerical modeling of the high temperature thermomechanical behavior of composite materials TRC at the mesoscale. In a first experimental part, the carbon textiles (commercial products on the market), the refractory concrete matrix and the textile/matrix interface were tested at constant temperature thermomechanical regime (ranging from 25 °C to 700 °C). The results obtained showed an effect of the textile treatment on the mechanical behavior and failure mode of the carbon textiles and the textile/matrix interface. An analytical model was also used to identify the evolution of thermomechanical properties of carbon textiles as a function of temperature. The thermal transfer in the cylindrical specimen was carried out to validate the thermal properties of refractory concrete. All results obtained in this part are used as input data for the numerical model in the modeling part. The second experimental part explores the thermomechanical behavior of TRCs under two regimes: thermomechanical at constant temperature and thermomechanical at constant force. Two carbon textiles, which gave the best performance at high temperature, were chosen for the manufacture of TRCs. The experimental results showed a hardening behavior with three or two phases at moderate temperature and a brittle behavior at higher temperature of 500 °C. In thermomechanical regime at constant force, two TRC composites can resist longer than carbon textiles alone thanks to good thermal insulation of refractory matrix. By comparing the two results on the TRC specimens, the effect of textile reinforcement (reinforcement ratio, treatment product and textile geometry) on the thermomechanical behavior was analyzed. All the experimental results of this part were used to validate and compare with those obtained from the numerical model. The purpose of the numerical modeling part is to predict the global thermomechanical

For ecological reasons, the current main challenge of the automotive industry is to reduce the fuel consumption of vehicles and then emissions of greenhouse gas. In this context, steelmakers and automotive manufacturers decided for some years now to join their efforts to promote the development and use of advanced high strength steels such as TRIP steels. A combination of high strength and large elongation is obtained thanks to the TRansformation Induced Plasticity (TRIP) effect. However, improvement of the mechanical properties is still possible, especially by the refinement of the matrix. In this work, two main ways were followed in order to reach improved properties. The classical way consisting of the annealing of cold-rolled samples and an innovative way consisting of obtaining the desired microstructure by direct hot rolling of the samples. In the classical way, this refinement can be obtained by acting on the chemical composition (with such alloying elements like Cu and Nb). It was observed that complete recrystallisation of the ferrite matrix is quite impossible in presence of Cu precipitates. In addition, if the ferrite recrystallisation is not completed before reaching the eutectoid temperature, the recrystallisation will be slowed down by a large way. An innovative heat treatment consisting in keeping the copper in solid solution in the high-Cu steel was developed. Therefore, ferrite recrystallises quite easily and very fine ferrite grains (~1µm) were obtained. In the innovative way, the effects of hot-rolling conditions on TRIP-assisted multiphase steels are of major importance for industrial practice and could open new dimensions for the TRIP steels (i.e. thanks to precipitation mechanisms leading to additive strengthening). Impressive mechanical properties (true stress at maximum load of 1500 MPa and true strain at uniform elongation of 0.22) were obtained with a relatively easy thermomechanical process, the role played by Nb being essential.