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Numerous applications in the present day ranging from testing humidity in air to detecting miniscule quantities of potentially hazardous chemical and biological agents in the air or water supplies require the development of chemical sensors capable of analyte detection with high sensitivity and selectively. Further, it has become desirable to create lab-on-chip systems that can detect multiple chemical agents and allow for sampling and testing of environments at locations distant from conventional laboratory facilities. Current challenges in this area include design, development and characterization of low detection limit sensors, development of low-noise readout methods, positive identification of analytes and, identification and reduction of the effect of various noise sources - both intrinsic and extrinsic to the sensor. The current work examines the performance limits of a 10-cantilever piezoresistive microcantilever array (PµCA) sensor. The microcantilevers measure analyte concentration in terms of the surface stress associated with analyte binding to the functionalized cantilever surface. The design, fabrication, characterization and testing of this measurement platform is presented. A novel aspect of the sensors developed is the use of n-type doping which increases the sensitivity of the device by one order of magnitude. In addition, design rules for surface stress-based chemical sensors have been developed. Extensive thermal characterization of the piezoresistive microcantilevers has been performed for DC and AC electrical excitation and values of heat transfer coefficient for the associated microscale phenomena are reported. Further, a method of low-noise measurement of cantilever resistance has been developed based on phase-sensitive detection techniques and this has been integrated with a multiplexing circuit to measure piezoresistance change in multiple cantilevers. Finally, the two novel techniques of chemical sensing- double-sided sensing and thermal array-based sensing have been investigated. These methods are presented as a means of extending the applicability and functionality of piezoresistive microcantilever sensors for chemical sensing.

A study of the stability of bicontinuous nanoporous metals is presented. Atomic scale simulations are used to probe the dominant mechanisms of geometric relaxation in these materials. A method is presented for generating model bicontinuous metal / void structures for use in atomistic simulations of bicontinuous nanoporous solids. The structures are generated with periodic boundary conditions using a phase-field model to simulate the spinodal decomposition of an ideal system. One phase in the model is then associated with the pore volume while the other phase is associated with the metal ligaments. Small angle neutron scattering was used to quantitatively compare experimental samples to those generated by the phase field method. EAM results using model structures with experimentally accessible length scales are presented which demonstrate the potential of such simulations in understanding the behavior of nanoporous metals. Simulated relaxations of these structures, as well as the relaxation of model spherical clusters, indicate that the surface relaxation effect dominates the overall dimensional relaxation of np-metals post processing. Capillary effects play a secondary role in the overall relaxation. The simulation results presented also identify a maximum surface area to volume ratio necessary to maintain mechanical stability beyond which the pore structure collapses. / Ph. D.

Three models for surface stress loading effect on a micromechanical cantilever are proposed as concentrated moment acting at the free end (Model I), concentrated moment plus axial force acting at the free end (Model II), and uniformly distributed surface force acting along the microcantilever (Model III). Solution to Model I loading is based on the Stoney formula, assuming that the microcantilever is subjected to pure bending and deformed with a constant curvature. Model II takes into account the clamping effect in such a way that an additional axial force is introduced. The deflections resulting from Models I and II surface stress loading effect are solved by Euler-Bernoulli beam theory. In Model III, the effect of surface stress is modeled as uniformly distributed surface force that causes both uniformly distributed bending moment and axial force acting along the axis of the microcantilever. The energy method is then used to obtain the governing equation and boundary conditions for Model III displacement. Comparison of the results obtained by the three models with those by the finite element method and experiment indicates that Model III is the most realistic model for surface stress loading effect to obtain the deflection of a microcantilever. Model III for surface stress loading effect is then used to demonstrate the applications of a microcantilever in sensor technology through the measurement of tip deflection under an atomic adsorption as the source of surface stress. Dual attractive or repulsive characteristics of interactions between a pair of mercury atoms are described in terms of Lennard-Jones potential. The force per unit atomic spacing induced by the adjacent free surface atoms of a monolayer is then computed using the potential. The sensitivities of atomic spacing and monolayer thickness to the tip-deflection of a microcantilever are studied in this research. / Master of Science

This work develops a methodology for the FEM simulation of a multi-piece crankshaft. Various simulation models that include press-fit joint contact conditions and complex meshing schemes are examined in order to accurately capture details of the stress fields present at the stress concentration area (labeled as the SCA) on the edge of the press-fit. The maximum stress components are demonstrated to be of limited values (non-singular) and Hertzian in nature. To obtain the stress convergence sufficiently small elements, which can be determined using a 2-D axisymmetric model, are required at the vicinity of the SCA. The same level of mesh refinement is then used for large 3-D FEM models of the crankshaft geometry, to study the resulting behavior of the press-fit joint for the dynamic operating loads. However, it may not always be possible or practical, as some limits on the mesh refinement have to be imposed to obtain a reasonable computational time to run such models. Less complex 'equivalent' symmetrical FEM models are investigated to determine if these models can provide a sufficient level of accuracy at an acceptable computational effort. Such models may be useful as practical design tools, producing data to speed up the decision making process. The simulation results are compared to some test data for the stress state monitored in real crankshafts under operating conditions. 'Intuitive' design sensitivities to various crankshaft parameters are examined as well. The numerical tools and engineering rules developed in the thesis may be applied to systematically improve the design by extending the joint's life and/or load carrying capability.

This work develops a methodology for the FEM simulation of a multi-piece crankshaft. Various simulation models that include press-fit joint contact conditions and complex meshing schemes are examined in order to accurately capture details of the stress fields present at the stress concentration area (labeled as the SCA) on the edge of the press-fit. The maximum stress components are demonstrated to be of limited values (non-singular) and Hertzian in nature. To obtain the stress convergence sufficiently small elements, which can be determined using a 2-D axisymmetric model, are required at the vicinity of the SCA. The same level of mesh refinement is then used for large 3-D FEM models of the crankshaft geometry, to study the resulting behavior of the press-fit joint for the dynamic operating loads. However, it may not always be possible or practical, as some limits on the mesh refinement have to be imposed to obtain a reasonable computational time to run such models. Less complex 'equivalent' symmetrical FEM models are investigated to determine if these models can provide a sufficient level of accuracy at an acceptable computational effort. Such models may be useful as practical design tools, producing data to speed up the decision making process. The simulation results are compared to some test data for the stress state monitored in real crankshafts under operating conditions. 'Intuitive' design sensitivities to various crankshaft parameters are examined as well. The numerical tools and engineering rules developed in the thesis may be applied to systematically improve the design by extending the joint's life and/or load carrying capability.

abstract: This work investigates in-situ stress evolution of interfacial and bulk processes in electrochemical systems, and is divided into two projects. The first project examines the electrocapillarity of clean and CO-covered electrodes. It also investigates surface stress evolution during electro-oxidation of CO at Pt{111}, Ru/Pt{111} and Ru{0001} electrodes. The second project explores the evolution of bulk stress that occurs during intercalation (extraction) of lithium (Li) and formation of a solid electrolyte interphase during electrochemical reduction (oxidation) of Li at graphitic electrodes. Electrocapillarity measurements have shown that hydrogen and hydroxide adsorption are compressive on Pt{111}, Ru/Pt{111}, and Ru{0001}. The adsorption-induced surface stresses correlate strongly with adsorption charge. Electrocatalytic oxidation of CO on Pt{111} and Ru/Pt{111} gives a tensile surface stress. A numerical method was developed to separate both current and stress into background and active components. Applying this model to the CO oxidation signal on Ru{0001} gives a tensile surface stress and elucidates the rate limiting steps on all three electrodes. The enhanced catalysis of Ru/Pt{111} is confirmed to be bi-functional in nature: Ru provides adsorbed hydroxide to Pt allowing for rapid CO oxidation. The majority of Li-ion batteries have anodes consisting of graphite particles with polyvinylidene fluoride (PVDF) as binder. Intercalation of Li into graphite occurs in stages and produces anisotropic strains. As batteries have a fixed size and shape these strains are converted into mechanical stresses. Conventionally staging phenomena has been observed with X-ray diffraction and collaborated electrochemically with the potential. Work herein shows that staging is also clearly observed in stress. The Li staging potentials as measured by differential chronopotentiometry and stress are nearly identical. Relative peak heights of Li staging, as measured by these two techniques, are similar during reduction, but differ during oxidation due to non-linear stress relaxation phenomena. This stress relaxation appears to be due to homogenization of Li within graphite particles rather than viscous flow of the binder. The first Li reduction wave occurs simultaneously with formation of a passivating layer known as the solid electrolyte interphase (SEI). Preliminary experiments have shown the stress of SEI formation to be tensile (~+1.5 MPa). / Dissertation/Thesis / Deconvolution programm - see Appendix C / ECdata4 program - see Appendix C / Ph.D. Materials Science and Engineering 2011

abstract: The electrode-electrolyte interface in electrochemical environments involves the understanding of complex processes relevant for all electrochemical applications. Some of these processes include electronic structure, charge storage, charge transfer, solvent dynamics and structure and surface adsorption. In order to engineer electrochemical systems, no matter the function, requires fundamental intuition of all the processes at the interface. The following work presents different systems in which the electrode-electrolyte interface is highly important. The first is a charge storage electrode utilizing percolation theory to develop an electrode architecture producing high capacities. This is followed by Zn deposition in an ionic liquid in which the deposition morphology is highly dependant on the charge transfer and surface adsorption at the interface. Electrode Architecture: A three-dimensional manganese oxide supercapacitor electrode architecture is synthesized by leveraging percolation theory to develop a hierarchically designed tri-continuous percolated network. The three percolated phases include a faradaically-active material, electrically conductive material and pore-former templated void space. The micropores create pathways for ionic conductivity, while the nanoscale electrically conducting phase provides both bulk conductivity and local electron transfer with the electrochemically active phase. Zn Electrodeposition: Zn redox in air and water stable N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [C2nmm][NTf2] is presented. Under various conditions, characterization of overpotential, kinetics and diffusion of Zn species and morphological evolution as a function of overpotential and Zn concentration are analyzed. The surface stress evolution during Zn deposition is examined where grain size and texturing play significant rolls in compressive stress generation. Morphological repeatability in the ILs led to a novel study of purity in ionic liquids where it is found that surface adsorption of residual amine and chloride from the organic synthesis affect growth characteristics. The drivers of this work are to understand the processes occurring at the electrode-electrolyte interface and with that knowledge, engineer systems yielding optimal performance. With this in mind, the design of a bulk supercapacitor electrode architecture with excellent composite specific capacitances, as well as develop conditions producing ideal Zn deposition morphologies was completed. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011