Certain hydrogel forming de novo proteins that utilize different crosslinking methods are studied experimentally on a rheometer. The stress reaxation modulus of CRC, a telechelic, triblock protein, is shown to be that of a stretched exponential function with a value of β ≅ 0.5. The insertion of an integrin binding domain and changes in pH within the range 6.5–8.5 are shown not to significantly affect the resulting rheological behavior. A selective chemical crosslinker is used on CRC hydrogel systems and is shown to change the rheological behavior of the system to that of a combination of a chemically and physically crosslinked system. Chemically crosslinked hydrogels composed of W6, a wheat gluten-based protein, demonstrate a storage modulus weakly dependent on the angular frequency that is much greater than the loss modulus, with a modulus concentration dependence of c^9/4.

Porous ceramic-metal composites, or cermets, such as nickel zirconia (Ni-YSZ), are widely used as the anode material in solid oxide fuel cells (SOFC). These materials need to enable electrochemical reactions and provide the mechanical support for the layered cell structure. Thus, for the anode supported planar cells, the thermomechanical behavior of the porous cermet directly affects the reliability of the cell. Porous cermets can be viewed as three-phase composites with a random heterogeneous microstructure. While random in nature, the effective properties and overall behavior of such composites can still be linked to specific stochastic functions that describe the microstructure. The main objective of this research was to develop the relationship between the thermomechanical behavior of porous cermets and their random microstructure. The research consists of three components. First, a stochastic reconstruction scheme was developed for the three-phase composite. From this multiple realizations with identical statistical descriptors were constructed for analysis. Secondly, a finite element model was implemented to obtain the effective properties of interest including thermal expansion coefficient, thermal conductivity, and elastic modulus. Lastly, nonlinear material behaviors were investigated, such as damage, plasticity, and creep behavior. It was shown that the computational model linked the statistical features of the microstructure to its overall properties and behavior. Such a predictive computational tool will enable the design of SOFCs with higher reliability and lower costs.

Certain hydrogel forming de novo proteins that utilize different crosslinking methods are studied experimentally on a rheometer. The stress reaxation modulus of CRC, a telechelic, triblock protein, is shown to be that of a stretched exponential function with a value of β ≅ 0.5. The insertion of an integrin binding domain and changes in pH within the range 6.5–8.5 are shown not to significantly affect the resulting rheological behavior. A selective chemical crosslinker is used on CRC hydrogel systems and is shown to change the rheological behavior of the system to that of a combination of a chemically and physically crosslinked system. Chemically crosslinked hydrogels composed of W6, a wheat gluten-based protein, demonstrate a storage modulus weakly dependent on the angular frequency that is much greater than the loss modulus, with a modulus concentration dependence of c^9/4.

Considérons un cas d’étude dans lequel les données produites par différentes techniques ont été obtenues en divers points d’une masse rocheuse où les effets topographiques sont très probablement significatifs. Les mesures ont été effectuées pour la conception du réseau hydroélectrique. Le réseau comprend une conduite hydraulique ainsi qu’une nouvelle centrale souterraine placée à mi-parcours de la conduite et sera principalement creusé dans le granite. Les diverses données ont été intégrées à un modèle continu équivalent afin d’évaluer le champ de contrainte régional et ainsi d’extrapoler les résultats des divers tests au volume de masse rocheuse concerné par le plan hydroélectrique. L'intégration des essais in situ et du modèle permet de déterminer les variations spatiales du champ de contrainte. Il est ainsi possible d’identifier le mécanisme de chargement à l’origine du champ de contrainte mesuré ainsi que le comportement rhéologique à long terme du géomatériel équivalent considéré. / A case study is considered in which data produced by different techniques have been gathered in various locations within a rock mass in which topography effects are most likely significant. Measurements were performed for the design of a re-powering scheme that includes a new hydraulic conduit and an underground cavern that will primarily be excavated in granite. An integrated approach for extrapolating the results from the various in situ tests to the rock mass volume of interest for the hydroelectric power scheme is presented. This approach includes the development of an equivalent continuum mechanics model. The integration of in situ tests and numerical modelling enables to determine the stress spatial variation which helps ascertain the loading mechanism at the origin of the measured stress field as well as the long-term rheological behavior of the equivalent geomaterial under consideration.

Este trabalho tem como objetivo investigar a redução da relaxação por compressão de borracha acrílica modificada (ACM) irradiada por feixe de elétrons, através da caracterização de seu comportamento mecânico e de sua estrutura molecular. O material, nas condições original e irradiado, foi inicialmente submetido a ensaios uniaxiais de tração e espectroscopia por infravermelho com o objetivo de verificar a influência da irradiação EB em seu comportamento, eliminando a possibilidade de degradação do material, permitindo a continuidade dos estudos. Definidas as doses, novos corpos de prova foram irradiados e submetidos a ensaios uniaxiais, equibiaxiais de tensão e cisalhamento puro, gerando resultados que foram aplicados na simulação pelo método de elementos finitos, utilizando o modelo de comportamento elástico não-linear de Ogden, para predizer o comportamento do material em condições de compressão. Confirmado o aumento da tensão por compressão para mesmas deformações, com o aumento da dose de radiação, análises termogravimétricas e dinâmicas mecânicas foram realizadas para possibilitar o entendimento do fenômeno. Na fase final do trabalho ensaios de relaxação por compressão foram realizados, em diferentes níveis de deformação e temperatura, apresentando a redução da relaxação por compressão gerada pela radiação EB e quantificando tal influência combinada com outros fatores, através da aplicação dos resultados no método de Planejamento Fatorial 2k. / The aim of this work is to investigate the compression stress relaxation (CSR) decrease of modified acrylic rubber, irradiated by electron beam, through its mechanical behavior and molecular structure characterization. Uniaxial tensile test and infrared spectroscopy were carried out, on original and irradiated material conditions, to verify the influence of EB irradiation on ACM, and to eliminate the possibility of degradation caused by EB radiation. After to define the radiation doses, new ACM specimens were irradiated. Uniaxial, equibiaxial and planar shear tests generated experimental data, which were applied to simulate the non linear elastic behavior of the material, through finite elements method, using the Ogden Model. Confirmed the compression stress increase at same deformation level, caused by increasing of radiation dose, thermogravimetric and dynamic mechanical analysis were carried out in order to make possible to understand the behavior changes. In the final part of this work, compression stress relaxation experiments were carried out, at two deformation and temperature levels, with the purpose to validate the compression stress relaxation decrease caused by EB radiation, and to quantify such influence combined with other factors. The CSR decrease combined with other influence variables were studied through use of factorial design.

La relation entre les propriétés viscoélastiques complexes de liquides polymères et leur structure microscopique et la dynamique est une question clé dans la science des matériaux et de la biophysique. Les théories modernes de la dynamique des polymères et la rhéologie décrivent les aspects universels du comportement viscoélastique sur la base de l'idée que les enchevêtrements moléculaires confinent filaments individuels à une dimension, la dynamique diffusifs (reptation) dans le tube-comme les régions dans l'espace. Alors que le modèle de tube est validé par son succès, ses éléments constitutifs (les statistiques et la dynamique de l'axe du tube ou des chemins primitifs et de l'confinement "cage" de chaînes voisines) ne sont pas directement observables. (1) Nous présentons un vaste ensemble de résultats de simulation pour la relaxation des contraintes à l'équilibre et l'étape-tendues perles printemps polymères fondus (En collaboration avec: C. Svaneborg et GS Grest). Les données nous permettent d'explorer la dynamique de la chaîne et le module de la relaxation de cisaillement dans le régime plateau pour les chaînes avec Z~40 enchevêtrements et dans le régime de relaxation terminale pour Z~10. Nous avons effectué des tests sans paramètres de plusieurs modèles différents de tubes à l'aide de (Rouse) la mobilité connue des chaînes unentangled et la longueur d'enchevêtrement de fusion déterminé par l'analyse du chemin primitif de l'état microscopique topologique de nos systèmes. (2) Nous présentons une compréhension complète pour la détente des empêtré polymère linéaire fond que les liens de la dynamique et la théorie de Rouse tube par une interprétation dynamique qui s’appellel’analyse du chemin primitive. La chaîne primitive, qui est la moyenne d'ensemble des conformations de la chaîne, se rétrécit strictement d’après la dynamique Rouse jusqu'à ce qu'il renconte les obstacles formés par d'autres chaînes primitives. Le temps d'arrêt de la diminution peut être déterminée par l'argument que la zone balayée par la chaîne primitive sur une longueur de propagation de tension qui est égale à la taille du maille de filet du travail formé par les chaînes de primitives. Le processus physique avant l'heure d'arrêt est assez présenté par l'analyse du chemin primitif. Après le temps d'arrêt, les longueurs primitives seront rétrécites par la reptation et la fluctuation de la longueur de contour .Cette procedure peut être décrite comme la modèle du tube, par exemple, Likhtman-McLeish (LM) la théorie. (3) Nous constatons que la théorie sous-estime la relaxation LM module de cisaillement dû à un double comptage de l'effet de courte longueur d'onde (p> Z) dans les modes partie de relaxation de Rouse et en fonction de la trompe de mémoire μ (t). LM extrapolé μ (t) à la limite du continuum, ce qui entraîne une décroissance sur des échelles de temps inférieur au temps de l'intrication, où le mouvement de la chaîne primitive devrait être négligeable. Pour corriger cela, nous avons retiré de la partie de fluctuation contour longueur de μ (t) la contribution des modes avec un temps de relaxation plus court que le temps d'enchevêtrement. Nous trouvons un excellent accord entre nos données de simulation et la théorie LM modifiée en utilisant l'approximation reptation double pour la libération de contrainte, ce qui démonte que l'analyse du chemin primitif de la structure microscopique apporte du modèle de tube avec une puissance prédictive des processus dynamiques. L'utilisation de systèmes plus complexes pour le traitement de la libération de contrainte devrait conduire à un accord encore mieux. / The relation between the complex viscoelastic properties of polymer liquids and their microscopic structure and dynamics is a key issue in materials science and biophysics. Modern theories of polymer dynamics and rheology describe the universal aspects of the viscoelastic behavior based on the idea that molecular entanglements confine individual filaments to a one-dimensional, diffusive dynamics (reptation) in tube-like regions in space. While the tube model is validated through its success, its constituting elements (the statistics and dynamics of the tube axis or primitive paths and of the confining "cage" of neighboring chains) are not directly observable. (1) We present an extensive set of simulation results for the stress relaxation in equilibrium and step-strained bead-spring polymer melts (In cooperation with: C. Svaneborg and G. S. Grest). The data allow us to explore the chain dynamics and the shear relaxation modulus into the plateau regime for chains with Z~40 entanglements and into the terminal relaxation regime for Z~10. We have performed parameter-free tests of several different tube models by using the known (Rouse) mobility of unentangled chains and the melt entanglement length determined via the primitive path analysis of the microscopic topological state of our systems. (2) We present a full understanding for relaxation of entangled linear polymer melts that links the Rouse dynamics and tube theory via a dynamic interpretation of the so called primitive path analysis. The primitive chain, which is the ensemble average of the chain conformations, shrinks strictly following the Rouse dynamic until it encounters the obstacles formed by other primitive chains. The stop time of the shrinking can be determined by the argument that the area swept by the primitive chain over a tension propagation length is equal to the mesh size of the net work formed by the primitive chains. The physical process before the stop time is fairly presented by primitive path analysis. After the stop time, the primitive length shrinks via reptation and contour length fluctuation, which is well described by the tube theory, e.g. Likhtman-McLeish (LM) theory. (3) We find that the LM theory underestimates the shear relaxation modulus due to a double-counting of the effect of short-wavelength (p>Z) modes in Rouse relaxation part and in tube memory function μ(t). LM extrapolated μ(t) to the continuum limit, resulting a decay on time scales smaller than the entanglement time, where the motion of the primitive chain should be negligible. To correct this, we have removed from the contour length fluctuation part of μ(t) the contribution of modes with a relaxation time shorter than entanglement time. We find excellent agreement between our simulation data and the modified LM theory using the double reptation approximation for constraint release, which demonstrates that the primitive path analysis of the microscopic structure endows the tube model with predictive power for dynamical processes. The use of more elaborate schemes for treating constraint release should lead to even better agreement.

In respect of autogenous and drying shrinkage and the effects of relaxation creep during the hydration cycle, roller compacted concrete in dams has to date been universally assumed to behave in the same manner as conventional mass concrete, despite notional evidence to the contrary on prototype dam structures, particularly in respect of high-paste RCC. While the results of laboratory materials testing and associated early behaviour analyses for RCC have been published, no conclusive example exists in the public domain whereby predicted behaviour is confirmed through measured behaviour on a comprehensively-instrumented prototype dam structure. In his PhD thesis, Quentin Shaw presents evidence to indicate that the early behaviour of RCC, and particularly high quality, high-paste RCC in dams, is quite different to that of CVC. Referring to instrumentation records from Wolwedans and Knellpoort dams in South Africa, Çine Dam in Turkey, Wadi Dayqah Dam in Oman and Changuinola 1 Dam in Panama, indications of less than expected shrinkage and stress relaxation creep during the hydration cycle in the constituent RCC are documented. Taking the comprehensively-instrumented and monitored Wolwedans Dam, the actual materials behaviour of the constituent RCC is evaluated through the replication of the prototype behaviour on a finite element model. Through this analysis, it is clearly demonstrated that the level of shrinkage and stress relaxation creep that would be traditionally assumed in RCC simply did not occur. In fact, the analyses suggested that no shrinkage, or creep was apparent. The reasons for the different behaviour of high-paste RCC compared to CVC are subsequently explored. With Wadi Dayqah Dam as the only example evaluated where some drying shrinkage and/or stress relaxation creep was obviously apparent, the evident susceptibility of this lean RCC mix, with a high w/c ratio, a high content of non-cementitious fines, natural gravel aggregates, a high aggregate water absorption and placement in a very dry environment, is noted. However, it is considered to be the combination of a strong aggregate skeletal structure developed through roller compaction and a low w/c ratio that results in a particularly resilience in high-paste RCC to early shrinkage and creep. It is also recognised that temperature and gravity effects in an arch dam structure will tend to limit, or even eliminate containment stresses in the critical load-carrying upper section and that this will reduce the risk and impact of stress relaxation creep. Consequently, a new understanding of the early behaviour of RCC in large dams is presented, suggesting that a high quality RCC mix in an arch dam can be designed for a cumulative shrinkage and stress relaxation creep under the hydration cycle of approximately 20 microstrain, compared with a more traditionally accepted value of between 125 and 200 microstrain. The implications of these findings on the design of large RCC dams are demonstrated to be significant, particularly in respect of RCC arch dams. In addition, suggestions are made for the requirements in respect of RCC mix design for negligible shrinkage and creep, while an approach to combine the use of field measurement with structural modelling to predict and demonstrate actual RCC behaviour is briefly discussed. / Thesis (PhD)--University of Pretoria, 2011. / Civil Engineering / unrestricted

Certain hydrogel forming de novo proteins that utilize different crosslinking methods are studied experimentally on a rheometer. The stress reaxation modulus of CRC, a telechelic, triblock protein, is shown to be that of a stretched exponential function with a value of β ≅ 0.5. The insertion of an integrin binding domain and changes in pH within the range 6.5–8.5 are shown not to significantly affect the resulting rheological behavior. A selective chemical crosslinker is used on CRC hydrogel systems and is shown to change the rheological behavior of the system to that of a combination of a chemically and physically crosslinked system. Chemically crosslinked hydrogels composed of W6, a wheat gluten-based protein, demonstrate a storage modulus weakly dependent on the angular frequency that is much greater than the loss modulus, with a modulus concentration dependence of c^9/4.

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