Post-shock thermochemistry in hypervelocity CO2 and air flow

This work represents ongoing efforts to study high-enthalpy carbon dioxide flows in anticipation of the upcoming Mars Science Laboratory (MSL) and future missions to the red planet. The work is motivated by observed anomalies between experimental and numerical studies in hypervelocity impulse facilities for high enthalpy carbon dioxide flows. In this work, experiments are conducted in the Hypervelocity Expansion Tube (HET) which, by virtue of its flow acceleration process, exhibits minimal freestream dissociation in comparison to reflected shock tunnels. This simplifies the comparison with computational result as freestream dissociation and considerable thermochemical excitation can be neglected. Shock shapes of the MSL aeroshell and spherical geometries are compared with numerical simulations incorporating detailed CO2 thermochemical modeling. The shock stand-off distance has been identified in the past as sensitive to the thermochemical state and as such, is used here as an experimental measurable for comparison with CFD and two different theoretical models. It is seen that models based upon binary scaling assumptions are not applicable for the low-density, small-scale conditions of the current work. Mars Science Laboratory shock shapes at zero angle of attack are also in good agreement with available data from the LENS X expansion tunnel facility, confi rming results are facility-independent for the same type of flow acceleration, and indicating that the flow velocity is a suitable first-order matching parameter for comparative testing. In an e ffort to address surface chemistry issues arising from high-enthalpy carbon dioxide ground-test based experiments, spherical stagnation point and aeroshell heat transfer distributions are also compared with simulation. Very good agreement between experiment and CFD is seen for all shock shapes and heat transfer distributions fall within the non-catalytic and super-catalytic solutions. We also examine spatial temperature profiles in the non-equilibrium relaxation region behind a stationary shock wave in a hypervelocity air Mach 7.42 freestream. The normal shock wave is established through a Mach reflection from an opposing wedge arrangement. Schlieren images confirm that the shock con guration is steady and the location is repeatable. Emission spectroscopy is used to identify dissociated species and to make vibrational temperature measurements using both the nitric oxide and the hydroxyl radical A-X band sequences. Temperature measurements are presented at selected locations behind the normal shock. LIFBASE is used as the simulation spectrum software for OH temperature-fitting, however the need to access higher vibrational and rotational levels for NO leads to the use of an in-house developed algorithm. For NO, results demonstrate the contribution of higher vibrational and rotational levels to the spectra at the conditions of this study. Very good agreement is achieved between the experimentally measured NO vibrational temperatures and calculations performed using an existing state-resolved, three-dimensional forced harmonic oscillator thermochemical model. The measured NO A-X vibrational temperatures are significantly higher than the OH A-X temperatures.

Shape and chemically anisotropic colloidal particles: A theoretical study of their structure, phase behavior, and slow dynamics

A detailed non-equilibrium state diagram of shape-anisotropic particle fluids is constructed. The effects of particle shape are explored using Naive Mode Coupling Theory (NMCT), and a single particle Non-linear Langevin Equation (NLE) theory. The dynamical behavior of non-ergodic fluids are discussed. We employ a rotationally frozen approach to NMCT in order to determine a transition to center of mass (translational) localization. Both ideal and kinetic glass transitions are found to be highly shape dependent, and uniformly increase with particle dimensionality. The glass transition volume fraction of quasi 1- and 2- dimensional particles fall monotonically with the number of sites (aspect ratio), while 3-dimensional particles display a non-monotonic dependence of glassy vitrification on the number of sites. Introducing interparticle attractions results in a far more complex state diagram. The ideal non-ergodic boundary shows a glass-fluid-gel re-entrance previously predicted for spherical particle fluids. The non-ergodic region of the state diagram presents qualitatively different dynamics in different regimes. They are qualified by the different behaviors of the NLE dynamic free energy. The caging dominated, repulsive glass regime is characterized by long localization lengths and barrier locations, dictated by repulsive hard core interactions, while the bonding dominated gel region has short localization lengths (commensurate with the attraction range), and barrier locations. There exists a small region of the state diagram which is qualified by both glassy and gel localization lengths in the dynamic free energy. A much larger (high volume fraction, and high attraction strength) region of phase space is characterized by short gel-like localization lengths, and long barrier locations. The region is called the attractive glass and represents a 2-step relaxation process whereby a particle first breaks attractive physical bonds, and then escapes its topological cage. The dynamic fragility of fluids are highly particle shape dependent. It increases with particle dimensionality and falls with aspect ratio for quasi 1- and 2- dimentional particles. An ultralocal limit analysis of the NLE theory predicts universalities in the behavior of relaxation times, and elastic moduli. The equlibrium phase diagram of chemically anisotropic Janus spheres and Janus rods are calculated employing a mean field Random Phase Approximation. The calculations for Janus rods are corroborated by the full liquid state Reference Interaction Site Model theory. The Janus particles consist of attractive and repulsive regions. Both rods and spheres display rich phase behavior. The phase diagrams of these systems display fluid, macrophase separated, attraction driven microphase separated, repulsion driven microphase separated and crystalline regimes. Macrophase separation is predicted in highly attractive low volume fraction systems. Attraction driven microphase separation is charaterized by long length scale divergences, where the ordering length scale determines the microphase ordered structures. The ordering length scale of repulsion driven microphase separation is determined by the repulsive range. At the high volume fractions, particles forgo the enthalpic considerations of attractions and repulsions to satisfy hard core constraints and maximize vibrational entropy. This results in site length scale ordering in rods, and the sphere length scale ordering in Janus spheres, i.e., crystallization. A change in the Janus balance of both rods and spheres results in quantitative changes in spinodal temperatures and the position of phase boundaries. However, a change in the block sequence of Janus rods causes qualitative changes in the type of microphase ordered state, and induces prominent features (such as the Lifshitz point) in the phase diagrams of these systems. A detailed study of the number of nearest neighbors in Janus rod systems reflect a deep connection between this local measure of structure, and the structure factor which represents the most global measure of order.