AN ENTROPIC THEORY OF DAMAGE WITH APPLICATIONS TO CORROSION-FATIGUE STRUCTURAL INTEGRITY ASSESSMENT

This dissertation demonstrates an explanation of damage and reliability of critical components and structures within the second law of thermodynamics. The approach relies on the fundamentals of irreversible thermodynamics, specifically the concept of entropy generation due to materials degradation as an index of damage. All failure mechanisms that cause degradation, damage accumulation and ultimate failure share a common feature, namely energy dissipation. Energy dissipation, as a fundamental measure for irreversibility in a thermodynamic treatment of non-equilibrium processes, leads to and can be expressed in terms of entropy generation. The dissertation proposes a theory of damage by relating entropy generation to energy dissipation via generalized thermodynamic forces and thermodynamic fluxes that formally describes the resulting damage. Following the proposed theory of entropic damage, an approach to reliability and integrity characterization based on thermodynamic entropy is discussed. It is shown that the variability in the amount of the thermodynamic-based damage and uncertainties about the parameters of a distribution model describing the variability, leads to a more consistent and broader definition of the well know time-to-failure distribution in reliability engineering. As such it has been shown that the reliability function can be derived from the thermodynamic laws rather than estimated from the observed failure histories. Furthermore, using the superior advantages of the use of entropy generation and accumulation as a damage index in comparison to common observable markers of damage such as crack size, a method is proposed to explain the prognostics and health management (PHM) in terms of the entropic damage. The proposed entropic-based damage theory to reliability and integrity is then demonstrated through experimental validation. Using this theorem, the corrosion-fatigue entropy generation function is derived, evaluated and employed for structural integrity, reliability assessment and remaining useful life (RUL) prediction of Aluminum 7075-T651 specimens tested.

CONTROL OF SIZE AND MAGNETIC PROPERTIES OF CARBOXYL-FUNCTIONALIZED MAGNETITE PARTICLES: SYNTHESIS PROCEDURES, CHARACTERIZATIONS, AND APPLICATIONS

Magnetic nanoparticles (MNPs) are known for the unique properties conferred by their small size and have found wide application in food safety analyses. However, their high surface energy and strong magnetization often lead to aggregation, compromising their functions. In this study, iron oxide magnetic particles (MPs) over the range of nano to micro size were synthesized, from which particles with less aggregation and excellent magnetic properties were obtained. MPs were synthesized via three different hydrothermal procedures, using poly (acrylic acid) (PAA) of different molecular weight (Mw) as the stabilizer. The particle size, morphology, and magnetic properties of the MPs from these synthesis procedures were characterized and compared. Among the three syntheses, one-step hydrothermal synthesis demonstrated the highest yield and most efficient magnetic collection of the resulting PAA-coated magnetic microparticles (PAA-MMPs, >100 nm). Iron oxide content of these PAA-MMPs was around 90%, and the saturation magnetization ranged from 70.3 emu/g to 57.0 emu/g, depending on the Mw of PAA used. In this approach, the particles prepared using PAA with Mw of 100K g/mol exhibited super-paramagnetic behavior with ~65% lower coercivity and remanence compared to others. They were therefore less susceptible to aggregation and remained remarkably water-dispersible even after one-month storage. Three applications involving PAA-MMPs from one-step hydrothermal synthesis were explored: food proteins and enzymes immobilization, antibody conjugation for pathogen capture, and magnetic hydrogel film fabrication. These studies demonstrated their versatile functions as well as their potential applications in the food science area.

SOVLENT REACTIVITY AND INTERFACE EVOLUTION AT MODEL ELECTRODES FOR ENERGY APPLICATIONS

The Li-ion rechargeable battery (LIB) is widely used as an energy storage device, but has significant limitations in battery cycle life and safety. During initial charging, decomposition of the ethylene carbonate (EC)-based electrolytes of the LIB leads to the formation of a passivating layer on the anode known as the solid electrolyte interphase (SEI). The formation of an SEI has great impact on the cycle life and safety of LIB, yet mechanistic aspects of SEI formation are not fully understood. In this dissertation, two surface science model systems have been created under ultra-high vacuum (UHV) to probe the very initial stage of SEI formation at the model carbon anode surfaces of LIB. The first model system, Model System I, is an lithium-carbonate electrolyte/graphite C(0001) system. I have developed a temperature programmed desorption/temperature programmed reaction spectroscopy (TPD/TPRS) instrument as part of my dissertation to study Model System I in quantitative detail. The binding strengths and film growth mechanisms of key electrolyte molecules on model carbon anode surfaces with varying extents of lithiation were measured by TPD. TPRS was further used to track the gases evolved from different reduction products in the early-stage SEI formation. The branching ratio of multiple reaction pathways was quantified for the first time and determined to be 70.% organolithium products vs. 30% inorganic lithium product. The obtained branching ratio provides important information on the distribution of lithium salts that form at the very onset of SEI formation. One of the key reduction products formed from EC in early-stage SEI formation is lithium ethylene dicarbonate (LEDC). Despite intensive studies, the LEDC structure in either the bulk or thin-film (SEI) form is unknown. To enable structural study, pure LEDC was synthesized and subject to synchrotron X-ray diffraction measurements (bulk material) and STM measurements (deposited films). To enable studies of LEDC thin films, Model System II, a lithium ethylene dicarbonate (LEDC)-dimethylformamide (DMF)/Ag(111) system was created by a solution microaerosol deposition technique. Produced films were then imaged by ultra-high vacuum scanning tunneling microscopy (UHV-STM). As a control, the dimethylformamide (DMF)-Ag(111) system was first prepared and its complex 2D phase behavior was mapped out as a function of coverage. The evolution of three distinct monolayer phases of DMF was observed with increasing surface pressure — a 2D gas phase, an ordered DMF phase, and an ordered Ag(DMF)2 complex phase. The addition of LEDC to this mixture, seeded the nucleation of the ordered DMF islands at lower surface pressures (DMF coverages), and was interpreted through nucleation theory. A structural model of the nucleation seed was proposed, and the implication of ionic SEI products, such as LEDC, in early-stage SEI formation was discussed.

Motion Planning and Controls with Safety and Temporal Constraints

Motion planning, or trajectory planning, commonly refers to a process of converting high-level task specifications into low-level control commands that can be executed on the system of interest. For different applications, the system will be different. It can be an autonomous vehicle, an Unmanned Aerial Vehicle(UAV), a humanoid robot, or an industrial robotic arm. As human machine interaction is essential in many of these systems, safety is fundamental and crucial. Many of the applications also involve performing a task in an optimal manner within a given time constraint. Therefore, in this thesis, we focus on two aspects of the motion planning problem. One is the verification and synthesis of the safe controls for autonomous ground and air vehicles in collision avoidance scenarios. The other part focuses on the high-level planning for the autonomous vehicles with the timed temporal constraints. In the first aspect of our work, we first propose a verification method to prove the safety and robustness of a path planner and the path following controls based on reachable sets. We demonstrate the method on quadrotor and automobile applications. Secondly, we propose a reachable set based collision avoidance algorithm for UAVs. Instead of the traditional approaches of collision avoidance between trajectories, we propose a collision avoidance scheme based on reachable sets and tubes. We then formulate the problem as a convex optimization problem seeking control set design for the aircraft to avoid collision. We apply our approach to collision avoidance scenarios of quadrotors and fixed-wing aircraft. In the second aspect of our work, we address the high level planning problems with timed temporal logic constraints. Firstly, we present an optimization based method for path planning of a mobile robot subject to timed temporal constraints, in a dynamic environment. Temporal logic (TL) can address very complex task specifications such as safety, coverage, motion sequencing etc. We use metric temporal logic (MTL) to encode the task specifications with timing constraints. We then translate the MTL formulae into mixed integer linear constraints and solve the associated optimization problem using a mixed integer linear program solver. We have applied our approach on several case studies in complex dynamical environments subjected to timed temporal specifications. Secondly, we also present a timed automaton based method for planning under the given timed temporal logic specifications. We use metric interval temporal logic (MITL), a member of the MTL family, to represent the task specification, and provide a constructive way to generate a timed automaton and methods to look for accepting runs on the automaton to find an optimal motion (or path) sequence for the robot to complete the task.