Statics, dynamics, rheology and scission-recombination kinetics of self-assembling linear micelles are investigated at equlibrium state and under shear flow by computer simulations using a newly proposed mesoscopic model. We model the micelles as linear sequences of Brownian beads whose space-time evolution is governed by Langevin dynamics. A Monte Carlo algorithm controls the opening of a bond or the chain-end fusion. A kinetic parameter omega modelling the effect of a potential barrier along a kinetic path, is introduced in our model. For equilibrium state we focus on the analysis of short and long time behaviors of the scission and recombination mechanisms. Our results show that at time scales larger than the life time of the average chain length, the kinetics is in agreement with the mean-field kinetics model of Cates. By studying macroscopic relaxation phenomena such as the average micelle length evolution after a T-jump, the monomer diffusion, and the zero shear relaxation function, we confirm that the effective kinetic constants found are indeed the relevant parameters when macroscopic relaxation is coupled to the kinetics of micelles. For the non-equilibrium situation, we study the coupled effects of the shear flow and the scission-recombination kinetics, on the structural and rheological properties of this micellar system. Our study is performed in semi-dilute and dynamically unentangled regime conditions. The explored parameter omega range is chosen in order for the life time of the average size chain to remain shorter than its intrinsic (Rouse) longest relaxation time. Central to our analysis is the concept of dynamical unit of size Lambda, the chain fragment for which the life time tau_Lambda and the Rouse time are equal. Shear thinning, chain gyration tensor anisotropy, chain orientation and bond stretching are found to depend upon the reduced shear rate Beta_Lambda=gamma dot*tau_Lambda while the average micelle size is found to decrease with increasing shear rate, independently of the height of the barrier of the scission-recombination process.

La viscosité est une propriété fondamentale des fluides complexes et qui reste encore difficile à prédire quantitativement. Cette propriété macroscopique provient de propriétés moléculaires et mésoscopiques. La compréhension et l’estimation de l'évolution de la viscosité avec des paramètres variables est important pour plusieurs applications, entre autres pour l’extraction liquide-liquide et pour la formulation de systèmes tensioactifs aqueux.Dans ce travail, un modèle "minimal" prenant en compte les énergies libres mises en jeu a été développé pour aider à comprendre, contrôler et prédire l'évolution de la viscosité des microémulsions en présence de solutés. Le terme «minimal» signifie dans ce contexte que ce modèle est basé sur un ensemble minimal de paramètres qui sont tous mesurables ou ont une signification physique, ce qui permet d’éviter le recours à des paramètres ajustables. Ce modèle développé dans cette thèse considère les termes chimiques à l'échelle moléculaire, les termes physiques à l'échelle mésoscopique ainsi que les caractéristiques d'écoulement à l'échelle macroscopique a été appliqué sur des microémulsions pauvres en eau utilisé pour l’extraction des métaux ainsi que sur des systèmes tensioactifs anioniques aqueux. / Viscosity is a fundamental property of complex fluids that is still nowadays extremely difficult to predict quantitatively. This macroscopic property originates from molecular and mesoscopic properties. The understanding and prediction of the evolution of the viscosity with changing parameters is crucial for several applications, amongst others for liquid-liquid extraction processes and for formulation of aqueous surfactant systems.In this work, a “minimal” model taking into account the relevant free energies was developed that helps to understand, control and predict the evolution of the viscosity of microemulsions in presence of solutes. The term “minimal” means in that context that this model is based on a minimal set of parameters that are all measurable and have a physical meaning, thus avoiding input of any adjustable parameter. This model that considers the chemical terms at molecular scale, the physical terms at meso-scale as well as the flow characteristics at macroscale was applied on water-poor extracting microemulsions as well as on aqueous anionic surfactant systems.

Statics, dynamics, rheology and scission-recombination kinetics of self-assembling linear micelles are investigated at equlibrium state and under shear flow by computer simulations using a newly proposed mesoscopic model. We model the micelles as linear sequences of Brownian beads whose space-time evolution is governed by Langevin dynamics. A Monte Carlo algorithm controls the opening of a bond or the chain-end fusion. A kinetic parameter omega modelling the effect of a potential barrier along a kinetic path, is introduced in our model.<p>For equilibrium state we focus on the analysis of short and long time behaviors of the scission and recombination mechanisms. Our results show that at time scales larger than the life time of the average chain length, the kinetics is in agreement with the mean-field kinetics model of Cates. By studying macroscopic relaxation phenomena such as the average micelle length evolution after a T-jump, the monomer diffusion, and the zero shear relaxation function, we confirm that the effective kinetic constants found are indeed the relevant parameters when macroscopic relaxation is coupled to the kinetics of micelles.<p>For the non-equilibrium situation, we study the coupled effects of the shear flow and the scission-recombination kinetics, on the structural and rheological properties of this micellar system. Our study is performed in semi-dilute and dynamically unentangled regime conditions. The explored parameter omega range is chosen in order for the life time of the average size chain to remain shorter than its intrinsic (Rouse) longest relaxation time. Central to our analysis is the concept of dynamical unit of size Lambda, the chain fragment for which the life time tau_Lambda and the Rouse time are equal. Shear thinning, chain gyration tensor anisotropy, chain orientation and bond stretching are found to depend upon the reduced shear rate Beta_Lambda=gamma dot*tau_Lambda while the average micelle size is found to decrease with increasing shear rate, independently of the height of the barrier of the scission-recombination process. / Doctorat en sciences, Spécialisation physique / info:eu-repo/semantics/nonPublished