No description available.

Detonation waves in gases are very complex, involving a highly transient cellular structure and a turbulent reaction zone coupled with transverse shocks. The role of out-of-equilibrium phenomena in these waves remains unclear despite extensive research on the underlying physics. On the small scales, translational non-equilibrium associated with shocks, as postulated by Zel’dovich, may significantly affect the chemistry, and these effects are not yet fully understood. Similarly, very fast chemical processes may involve out-of-equilibrium effects due to local energy release that has been postulated by Prigogine. On larger scales, detonation waves display a cellular structure and are supported by turbulent combustion. The present thesis aims to quantify the importance of these three out-of-equilibrium effects on ignition, wave amplification, and diffraction limits of detonations. First, the role of translational non-equilibrium in reactive dynamics in the thermal explosion problem is investigated using molecular dynamics (MD) simulations and continuum models. Ignition delays are calculated and compared with rates from kinetic theory. MD results show agreement with the Prigogine and Mahieu corrections to the reaction rate evaluated from kinetic theory assuming a Maxwell-Boltzmann distribution. Accounting for the departure from translational equilibrium was found to reduce the ignition delay by up to 30% specifically at high activation energies. However, at low activation energies, the standard equilibrium rate shows a longer delay by up to 60%. The molecular dynamics simulations reveal that translational non-equilibrium effects accelerate activated exothermic reactions, referred to as “molecular hotspots”. The second part of the study focuses on the impact of thermal non-equilibrium and its coupling with reactive kinetics in shock-to-detonation transitions in gases. Results suggest that shock-induced ignition and transition to detonation involve non-equilibrium reactions that overlap with the shock structure, showing strong translational non-equilibrium with reactive fingers. Comparison with continuum simulations using different approximations reveals that shock amplification rate and transition to detonation are approximately twice as fast as predicted by conventional Euler hydrodynamic models, despite evidence of non-equilibrium. A Navier-Stokes model with hard sphere transport properties effectively captures the acceleration process, indicating significant implications for modeling gaseous detonations with fast reactions and strongly coupled pressure wave dynamics and reactivity in the detonation structure. In the last part of the thesis, the 3D hydrodynamic structure of cellular detonations is modeled by a global 1D mean hydrodynamic average model. Transport properties are artificially increased to account for the high-speed behavior resulting from fast turbulent diffusion. The existence of steady state Navier-Stokes detonation structure, as studied by Wood, is critically reviewed for this purpose and compared with transient calculations. Observations reveal that in the hyper-diffuse model, the shock and reaction zone overlap, resulting in a thickened reaction zone. The 1D model is used to study diffraction dynamics, with critical diffraction occurring when the tube diameter approaches the hydrodynamic reaction zone thickness. After diffraction, the complex viscous detonation structure separates, resulting in a rapid flame transitioning into a weak detonation. The conclusion of the present survey on the role of out-of-equilibrium effects on detonation dynamics suggests that non-equilibrium ignition due to molecular hotspots may give rise to corrections on the reaction rates by at most a factor of two. The coupling of exothermic reactions with the non-equilibrium structure of shock waves also predicts rates of shock amplification different by a factor of two from the standard Euler model for ignition, but accounting for the diffusive effects brings the MD and continuum predictions into closer agreement. Similarities with the out-of-equilibrium hydrodynamic structure of detonations are discussed.

This thesis investigates the underlying causes of friction and ine ciency within an internal combustion engine, focusing on the ring-liner conjunction in the vicinity of the power-stroke top dead centre reversal. In such lubricated contacts, friction is the result of the interplay between numerous kinetics, with those at micro- and nano-scale interactions being signi cantly di erent than the ones at larger scales. A modi ed Elrod's cavitation algorithm is developed to determine the microscopic tribological characteristics of the piston ring-liner contact. Predicting lubricant tran- sient behaviour is critical when the inlet reversal leads to thin lms and inherent metal-to-metal interaction. The model clearly shows that cavitation at the trailing edge of the ring-liner contact generated pre-reversal, persists after reversal and pro- motes starvation and depletion of the oil lm. Hence, this will lead to boundary friction. A fractal based boundary friction model is developed for lightly loaded asperity con- tacts, separated by diminishing small lms, usually wetted by a layer of molecules adsorbed to the tips of the asperities. In nano-scale conjunctions, a lubricant layering e ect often takes place due to the smoothness of surfaces, which is governed by the surface and lubricant properties. A molecularly thin layer of lubricant molecules can adhere to the asperities, being the last barrier against direct surface contact. As a result, boundary friction (prevailing in such diminishing gaps) is actually determined by a combination of shearing of a thin adsorbed lm, adhesion of approaching as- perities and their plastic deformation. A model for physio-chemical hydrodynamic mechanism is successfully established, describing the formation of thin adsorbed lms between asperities. This model is e ectively integrated with separately devel- oped models that predict the adhesive and plastic contact of asperities.

This thesis investigates the underlying causes of friction and ine ciency within an internal combustion engine, focusing on the ring-liner conjunction in the vicinity of the power-stroke top dead centre reversal. In such lubricated contacts, friction is the result of the interplay between numerous kinetics, with those at micro- and nano-scale interactions being signi cantly di erent than the ones at larger scales. A modi ed Elrod's cavitation algorithm is developed to determine the microscopic tribological characteristics of the piston ring-liner contact. Predicting lubricant tran- sient behaviour is critical when the inlet reversal leads to thin lms and inherent metal-to-metal interaction. The model clearly shows that cavitation at the trailing edge of the ring-liner contact generated pre-reversal, persists after reversal and pro- motes starvation and depletion of the oil lm. Hence, this will lead to boundary friction. A fractal based boundary friction model is developed for lightly loaded asperity con- tacts, separated by diminishing small lms, usually wetted by a layer of molecules adsorbed to the tips of the asperities. In nano-scale conjunctions, a lubricant layering e ect often takes place due to the smoothness of surfaces, which is governed by the surface and lubricant properties. A molecularly thin layer of lubricant molecules can adhere to the asperities, being the last barrier against direct surface contact. As a result, boundary friction (prevailing in such diminishing gaps) is actually determined by a combination of shearing of a thin adsorbed lm, adhesion of approaching as- perities and their plastic deformation. A model for physio-chemical hydrodynamic mechanism is successfully established, describing the formation of thin adsorbed lms between asperities. This model is e ectively integrated with separately devel- oped models that predict the adhesive and plastic contact of asperities.

The goal of this thesis is to study the role of single particle elasticity in the overall behavior of particulate systems. For this purpose, we use microgel particles, which are crosslinked polymer networks immersed in a solvent. In these systems, the amount of cross-linker determines their elasticity and ultimately the stiffness of the particle. For a system of hard spheres, the phase behavior is solely determined by the volume fraction occupied by the particles. Based on the volume fraction, liquid, crystal and glassy phases are observed. Interestingly, microgel particles display a richer and fascinating set of different behaviors depending on the particle stiffness. Previous results obtained in our group show that for highly cross-linked microgels, the glass phase disappears and there are only liquid and crystalline phases. By contrast, preliminary measurements indicate that for ultrasoft microgel particles the system does not show any signature of crystalline or glassy phases. The system seems to remain liquid irrespective of volume fractions. In this Thesis, we will address this striking result using light scattering as well as rheology, in order to access both static and dynamic properties in a wide range of length and time scales. In addition, we will also perform additional studies using very stiff microgels and use their swelling capabilities to change the volume fraction. We will use hydrostatic pressure to change the miscibility of the polymer network and thus change the microgel size; the use of this external variable allows fast equilibration times and homogeneous changes throughout the sample. By using neutron scattering techniques, we study the structural and dynamical properties of the system in its different phases involved.

No description available.

Dans cette thèse nous avons étudié de nombreux aspects de la théorie des systèmes désordonnés. En particulier, nous avons étudié les systèmes vitreux. La description détaillée des systèmes désordonnés et vitreux est un problème ouvert en physique de la matière condensée. Dans le cadre de la théorie de champ moyen pour les verres structuraux nous avons étudié la théorie des fluctuations proche de la transition vitreuse dynamique. L’étude des fluctuations peut etre fait avec le formalisme statique de la théorie de répliques. Nous avons fait cela en introduisant une théorie des champs pour la transition vitreuse à partir du potentiel microscopique entre les particules. Nous avons étudié dans ce cadre les fluctuations au niveau gaussien et nous avons évalués les exposants critiques dans ces approximations. Nous avons aussi étudié la région de validité de la prédiction gaussienne avec l’introduction d’un critère de Ginzburg pour la transition vitreuse. Les résultats que nous avons obtenues ne sont valides que dans la région β. Pour obtenir des resultats dans la région α nous avons étudié la pseudodynamique de Boltzmann que a été introduit par Franz and Parisi. Nous sommes parti des équations de Ornstein-Zernike et nous avons obtenu un ensemble d’équations dynamiques. En utilisant l’approximation Hypernetted Chain nous avons obtenu un ensemble complet d’équations qui sont très similaires aux équations de la théorie de mode-coupling. La troisième partie de la thèse porte sur l’étude des états amorphes des sphères dures en hautes dimensions. Pour obtenir les exposants dynamique dans ce cas, nous avons étudié la stabilité du diagramme de phase 1RSB (one-step-replica-symmetry-breaking). Nous avons découvert que ce diagramme de phase possède une région où la solution 1RSB est instable. La région où la solution 1RSB est instable est connectée avec la description théorique de la physique de jamming des sphères dures et nous avons montré que l’instabilité 1RSB est responsable d’une transition de phase en haute densité. Cette transition s’appelle la transition de Gardner. Nous avons cherché une solution 2RSB et nous avons vu qu’il existait un point en densité après lequel on peut avoir une solution 2RSB (et aussi fullRSB). Nous avons étudié le diagramme de phase 2RSB dans la limite de jamming où la pression devient infini. Après la solution 2RSB nous avons cherché à décrire la solution fullRSB. Nous avons écrit les équations fullRSB et nous avons découvert qu’elles sont identiques aux equations que l’on a dans le cas de un modèle de verres de spins qui s’appelle modèle de Sherrington et Kirkpatrick. Nous avons aussi étudié la solution numerique des équations fullRSB dans la limite de jamming. Cette solution montre beaucoup des choses intéressantes. La plus importante est le comportement du mean square displacement dans la limite de jamming. Si l’on regard les résultats numériques et éxperimentaux, il semble que le plateau de le mean square displacement s’approche a zero comme la pression à un exposant proche de −3/2. Nous avons vu que la solution numérique des équations fullRSB est en mesure de reproduire ce comportement. La quatrième partie de la thése a porté sur la dynamique de mode-coupling dans le régime où la transition vitreuse devient continue. / In this thesis we have studied many aspects of the physics of disordered and glassy systems. The first part of the work is about the theory of dynamical fluctuations in the beta regime. When a system undergoes a dynamical arrest, it can be studied by introducing an appropriate dynamical correlation function that plays the role of the order parameter of the transition. To understand the collective effects underlying the glass transition we have studied the fluctuations of the order parameter on a time scale where the system is relaxed in a typical metastable glassy state. To do this we have seen that coming from the glass phase the system develops critical fluctuations with a diverging correlation length at the mean field level. We have thus derived an effective field theory by focusing only on them. This field theory can be used firstly to derive the mode-coupling exponent parameter that controls the relaxation of the dynamical correlation function when the system relaxes in a metastable glassy state. Moreover we can give a Ginzburg Criterion that can be used to determine the region of validity of the Gaussian approximation. These considerations are valid in the beta regime. To clarify what happens in the alpha regime we have studied a quasi-equilibrium construction, called Boltzmann-Pseudodynamics, recently introduced in order to describe with static techniques the long time regime of glassy dynamics. We have extended this formalism to structural glasses by producing a new set of dynamical equations. We have done this in the simplest approximation scheme that is called Hypernetted Chain. Two results have been obtained : firstly, we have computed the mode-coupling exponent parameter and we have shown that it coincides with the one obtained with the formalism of the first part of the thesis ; secondly we have studied the aging regime and we have derived that the condition that determines the fluctuation-dissipation ratio is a marginal stability one. In the third part of the thesis we have studied the theory of amorphous states of hard spheres in high dimensions. Hard spheres provide simple models of glasses and they are extensively studied for the jamming transition. In our framework jammed states can be thought as infinite pressure limit of metastable glassy states. During the last years it has been derived a mean field theory of hard spheres based on the 1RSB assumption on the structure of the free energy landscape. However it has been realized that this construction is inconsistent for what concerns the property of the packings at jamming. In the present work we have firstly investigated the possibility of an instability of the 1RSB solution and we have actually found that the 1RSB solution is unstable in the jamming part of the phase diagram. At the same time we have been able to compute the mode-coupling exponent parameter for this system. In order to go beyond the 1RSB solution we have first tried a 2RSB ansatz and then a fullRSB solution. We have derived a set of variational equations that are very close to the ones that have been derived in the Sherrington-Kirkpatrick model. We have solved numerically the equations and we have shown that the fullRSB solution seems to predict that the plateau value of the mean square displacement scale as the pressure to a power close to 3/2 as it seems to be predicted by scaling arguments and in contrast with the 1RSB predictions that show a scaling with the inverse of the pressure. The last chapter of the thesis is on the mode-coupling theory when the glass transition is becoming continuous. We have been able to show that in such a situation a detailed characterization of the solution of the equations can be obtained in the long time regime.

No description available.

On considère l'évolution adiabatique des états vitreux sous perturbations extérieures. Bien que le formalisme que nous utilisons soit très général, nous nous concentrons ici sur les sphères dures en dimension infinie où une analyse exacte est possible. Nous considérons perturbations de la frontière, notamment compression ou cisaillement simple et nous calculons la réponse des états vitreux à ces perturbations : pression et contrainte de cisaillement. Nous constatons un dépassement des deux quantités avant que l'état vitreux ne devienne instable à un point spinodal, où il fond dans le liquide (ou cède). Nous estimons également la limite d'élasticité du verre. Enfin, nous étudions la stabilité des bassins vitreux vers la rupture en sous-bassins, correspondant à une transition de Gardner. Nous constatons que près de la transition dynamique, les verres subissent une transition de Gardner après une perturbation infinitésimale. Nous étudions ensuite le régime de haute pression et haut cisaillement au-delà de la transition de Gardner. / We consider the adiabatic evolution of glassy states under external perturbations. Although the formalism we use is very general, we focus here on infinite-dimensional hard spheres where an exact analysis is possible. We consider perturbations of the boundary, i. e. compression or (volume preserving) shear-strain, and we compute the response of glassy states to such perturbations: pressure and shear-stress. We find that both quantities over shoot before the glass state becomes unstable at a spinodal point where it melts into a liquid (or yields). We also estimate the yield stress of the glass. Finally, we study the stability of the glass basins towards breaking into sub-basins, corresponding to a Gardner transition. We find that close to the dynamical transition, glasses undergo a Gardner transition after an infinitesimal perturbation. We then study the high-pressure and high-strain regime beyond the Gardner transition.

Bulk metallic glasses represent a newly developed class of materials. Some metallic glasses possess combinations of very good or even excellent mechanical, chemical and/or magnetic properties uncovering a broad range of both industrial and vital applications. Besides all advantages metallic glasses have also significant drawbacks, which have to be overcome for commercial application. Apart from low critical thicknesses, brittleness and chemical inhomogeneity one important problem of metallic glasses is the lack of an appropriate theory describing their structure. Therefore, the search for new glass forming compositions as well as the improving of existing ones occurs at present by means of trial-and-error methods and a number of empirical rules. Empirical rules for good glass-forming ability of bulk metallic glasses have been established in recent years by Inoue and Egami. Two of these rules, (i) Preference of more than 3 elements and (ii) Need of more than 12 % radii difference of base elements, seem to be closely related to topological (geometrical) criteria. From this point of view topological parameters contribute essentially to the glass-forming ability. The third rule (iii) demands a negative mixing enthalpy of base elements and refers to the chemical interaction of the atoms. The generalized Bernal’s model (hard-sphere approximation) was used for the simulation of monatomic, binary and multi-component structures. Excluding chemical interaction, this method allows the investigation of topological criteria of the glass-forming ability. Bernal’s hard-sphere model was shown to be a good approximation for bulk metallic glasses and metallic liquids and yields good coincidence of experimental and theoretical results. • The Laguerre (weighted Voronoi) tessellation technique was used as the main tool for the structural analysis. Due to very complex structures it is impossible to determine the structure of bulk metallic glasses by means of standard crystallographic methods. • Density, radial distribution function, coordination number and Laguerre polyhedra analysis confirm amorphism of the simulated structures and are in a good agreement with available experimental results. • The ratio of the fractions of non-crystalline to crystalline Laguerre polyhedra faces was introduced as a new parameter . This parameter reflects the total non-crystallinity of a structure and the amount of atomic rearrangements necessary for crystallization. Thus, the parameter is related to the glass-forming ability. It depends strongly on composition and atomic size ratio and indicates a region of enhanced glass-forming ability in binary mixtures at 80 % of small atoms and atomic size ratio of 1.3. All found maxima of parameter for ternary mixtures have compositions and size ratios which are nearly the same as for the binary mixture with the maximum value of . • A new method of multiple-compression was introduces in order to test the tendency towards densification and/or crystallization of the simulated mixtures. The results of the multiple-compression of monatomic mixtures indicate a limiting value of about 0.6464 for the density of the amorphous state. Further densification is necessarily connected to formation and growth of nano-crystalline regions. • The results of the multiple-compression for binary mixtures shows a new maximum of the density at the size ratio of 1.3 and 30 % to 90 % of small atoms. This maximum indicates a local island of stability of the amorphous state. The maximal receivable density without crystallization in this region is enhanced compared to neighbouring regions. • The comparison of the parameter and the density to the distribution of known binary bulk metallic (metal-metal) glasses clearly shows that both parameters play a significant role in the glass-forming ability. • The polyhedra analysis shows regions with enhanced fraction of the icosahedral short-range order (polyhedron (0, 0, 12)) in the binary systems with the maximum at 80 % of small atoms and size ratio of 1.3. Comparison of the distribution of the (0, 0, 12) polyhedra to the distribution of known binary metallic (metal-metal) glasses and to the parameter shows that icosahedral short-range order is not related to the glass-forming ability and is a consequence of the high non-crystallinity (high values of ) of the mixtures and non vice versa. Results for the ternary mixtures confirm this observation. • A new approach for the calculation of the mixing enthalpy is proposed. The new method is based on the combination of Miedema’s semi-empirical model and Laguerre tessellation technique. The new method as well as 6 other methods including the original Miedema’s model were tested for more than 1400 ternary and quaternary alloys. The results show a better agreement with experimental values of the mixing enthalpy for the new model compared to all other methods. The new model takes into account the local structure at atom site and can be applied to all metallic alloys without additional extrapolations if the atomic structure of the considered alloy is known from a suitable atomistic structure model.