Hydrogen embrittlement (HE) is a phenomenon that affects both the physical and chemical properties of several intrinsically ductile metals. Consequently, understanding the mechanisms behind HE has been of particular interest in both experimental and modeling research. Discrepancies between experimental observations and modeling results have led to various proposals for HE mechanisms. Therefore, to gain insights into HE mechanisms in iron, this dissertation aims to investigate several key issues involving HE such as: a) the incipient crack tip events; b) the cohesive strength of grain boundaries (GBs); c) the dislocation-GB interactions and d) the dislocation mobility.

The crack tip, which presents a preferential trap site for hydrogen segregation, was examined using atomistic methods and the continuum based Rice-Thompson criterion as sufficient concentration of hydrogen can alter the crack tip deformation mechanism. Results suggest that there is a plausible co-existence of the adsorption induced dislocation emission and hydrogen enhanced decohesion mechanisms. In the case of GB-hydrogen interaction, we observed that the segregation of hydrogen along the interface leads to a reduction in cohesive strength resulting in intergranular failure. A methodology was further developed to quantify the role of the GB structure on this behavior.

GBs play a fundamental role in determining the strengthening mechanisms acting as an impediment to the dislocation motion; however, the presence of an unsurmountable barrier for a dislocation can generate slip localization that could further lead to intergranular crack initiation. It was found that the presence of hydrogen increases the strain energy stored within the GB which could lead to a transition in failure mode. Finally, in the case of body centered cubic metals, understanding the complex screw dislocation motion is critical to the development of an accurate continuum description of the plastic behavior. Further, the presence of hydrogen has been shown to drastically alter the plastic deformation, but the precise role of hydrogen is still unclear. Thus, the role of hydrogen on the dislocation mobility was examined using density functional theory and atomistic simulations. Overall, this dissertation provides a novel atomic-scale understanding of the HE mechanism and development of multiscale tools for future endeavors.

In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles with macroscopic wavelengths are not technologically useful; over the past decade or so, however, thanks to the widespread availability of soft polymers and silicone materials micro-buckles with wavelengths in submicron to micron scale have received increasing attention because it is useful for generating well-ordered periodic microstructures spontaneously without conventional lithographic techniques. This thesis investigates the buckling behavior of thin stiff films on soft polymeric substrates and explores a variety of applications, ranging from optical gratings, optical masks, energy harvest to energy storage. A laser scanning technique is proposed to detect micro-strain induced by thermomechanical loads and a periodic buckling microstructure is employed as a diffraction grating with broad wavelength tunability, which is spontaneously generated from a metallic thin film on polymer substrates. A mechanical strategy is also presented for quantitatively buckling nanoribbons of piezoelectric material on polymer substrates involving the combined use of lithographically patterning surface adhesion sites and transfer printing technique. The precisely engineered buckling configurations provide a route to energy harvesters with extremely high levels of stretchability. This stiff-thin-film/polymer hybrid structure is further employed into electrochemical field to circumvent the electrochemically-driven stress issue in silicon-anode-based lithium ion batteries. It shows that the initial flat silicon-nanoribbon-anode on a polymer substrate tends to buckle to mitigate the lithiation-induced stress so as to avoid the pulverization of silicon anode. Spontaneously generated submicron buckles of film/polymer are also used as an optical mask to produce submicron periodic patterns with large filling ratio in contrast to generating only ~100 nm edge submicron patterns in conventional near-field soft contact photolithography. This thesis aims to deepen understanding of buckling behavior of thin films on compliant substrates and, in turn, to harness the fundamental properties of such instability for diverse applications.

ABSTRACT Electronics especially mobile electronics such as smart phones, tablet PCs, notebooks and digital cameras are undergoing rapid development nowadays and have thoroughly changed our lives. With the requirement of more transistors, higher power, smaller size, lighter weight and even bendability, thermal management of these devices became one of the key challenges. Compared to active heat management system, heat pipe, which is a passive fluidic system, is considered promising to solve this problem. However, traditional heat pipes have size, weight and capillary limitation. Thus new type of heat pipe with smaller size, lighter weight and higher capillary pressure is needed. Nanofiber has been proved with superior properties and has been applied in multiple areas. This study discussed the possibility of applying nanofiber in heat pipe as new wick structure. In this study, a needleless electrospinning device with high productivity rate was built onsite to systematically investigate the effect of processing parameters on fiber properties as well as to generate nanofiber mat to evaluate its capability in electronics cooling. Polyethylene oxide (PEO) and Polyvinyl Alcohol (PVA) nanofibers were generated. Tensiometer was used for wettability measurement. The results show that independent parameters including spinneret type, working distance, solution concentration and polymer type are strongly correlated with fiber morphology compared to other parameters. The results also show that the fabricated nanofiber mat has high capillary pressure.

Structural health management (SHM) is emerging as a vital methodology to help engineers improve the safety and maintainability of critical structures. SHM systems are designed to reliably monitor and test the health and performance of structures in aerospace, civil, and mechanical engineering applications. SHM combines multidisciplinary technologies including sensing, signal processing, pattern recognition, data mining, high fidelity probabilistic progressive damage models, physics based damage models, and regression analysis. Due to the wide application of carbon fiber reinforced composites and their multiscale failure mechanisms, it is necessary to emphasize the research of SHM on composite structures. This research develops a comprehensive framework for the damage detection, localization, quantification, and prediction of the remaining useful life of complex composite structures. To interrogate a composite structure, guided wave propagation is applied to thin structures such as beams and plates. Piezoelectric transducers are selected because of their versatility, which allows them to be used as sensors and actuators. Feature extraction from guided wave signals is critical to demonstrate the presence of damage and estimate the damage locations. Advanced signal processing techniques are employed to extract robust features and information. To provide a better estimate of the damage for accurate life estimation, probabilistic regression analysis is used to obtain a prediction model for the prognosis of complex structures subject to fatigue loading. Special efforts have been applied to the extension of SHM techniques on aerospace and spacecraft structures, such as UAV composite wings and deployable composite boom structures. Necessary modifications of the developed SHM techniques were conducted to meet the unique requirements of the aerospace structures. The developed SHM algorithms are able to accurately detect and quantify impact damages as well as matrix cracking introduced.

Pb-free solders are used as interconnects in various levels of micro-electronic packaging. Reliability of these interconnects is very critical for the performance of the package. One of the main factors affecting the reliability of solder joints is the presence of porosity which is introduced during processing of the joints. In this thesis, the effect of such porosity on the deformation behavior and eventual failure of the joints is studied using Finite Element (FE) modeling technique. A 3D model obtained by reconstruction of x-ray tomographic image data is used as input for FE analysis to simulate shear deformation and eventual failure of the joint using ductile damage model. The modeling was done in ABAQUS (v 6.10). The FE model predictions are validated with experimental results by comparing the deformation of the pores and the crack path as predicted by the model with the experimentally observed deformation and failure pattern. To understand the influence of size, shape, and distribution of pores on the mechanical behavior of the joint four different solder joints with varying degrees of porosity are modeled using the validated FE model. The validation technique mentioned above enables comparison of the simulated and actual deformation only. A more robust way of validating the FE model would be to compare the strain distribution in the joint as predicted by the model and as observed experimentally. In this study, to enable visualization of the experimental strain for the 3D microstructure obtained from tomography, a three dimensional digital image correlation (3D DIC) code has been implemented in MATLAB (MathWorks Inc). This developed 3D DIC code can be used as another tool to verify the numerical model predictions. The capability of the developed code in measuring local displacement and strain is demonstrated by considering a test case.

Damage detection in heterogeneous material systems is a complex problem and requires an in-depth understanding of the material characteristics and response under varying load and environmental conditions. A significant amount of research has been conducted in this field to enhance the fidelity of damage assessment methodologies, using a wide range of sensors and detection techniques, for both metallic materials and composites. However, detecting damage at the microscale is not possible with commercially available sensors. A probable way to approach this problem is through accurate and efficient multiscale modeling techniques, which are capable of tracking damage initiation at the microscale and propagation across the length scales. The output from these models will provide an improved understanding of damage initiation; the knowledge can be used in conjunction with information from physical sensors to improve the size of detectable damage. In this research, effort has been dedicated to develop multiscale modeling approaches and associated damage criteria for the estimation of damage evolution across the relevant length scales. Important issues such as length and time scales, anisotropy and variability in material properties at the microscale, and response under mechanical and thermal loading are addressed. Two different material systems have been studied: metallic material and a novel stress-sensitive epoxy polymer.

For metallic material (Al 2024-T351), the methodology initiates at the microscale where extensive material characterization is conducted to capture the microstructural variability. A statistical volume element (SVE) model is constructed to represent the material properties. Geometric and crystallographic features including grain orientation, misorientation, size, shape, principal axis direction and aspect ratio are captured. This SVE model provides a computationally efficient alternative to traditional techniques using representative volume element (RVE) models while maintaining statistical accuracy. A physics based multiscale damage criterion is developed to simulate the fatigue crack initiation. The crack growth rate and probable directions are estimated simultaneously.

Mechanically sensitive materials that exhibit specific chemical reactions upon external loading are currently being investigated for self-sensing applications. The "smart" polymer modeled in this research consists of epoxy resin, hardener, and a stress-sensitive material called mechanophore The mechanophore activation is based on covalent bond-breaking induced by external stimuli; this feature can be used for material-level damage detections. In this work Tris-(Cinnamoyl oxymethyl)-Ethane (TCE) is used as the cyclobutane-based mechanophore (stress-sensitive) material in the polymer matrix. The TCE embedded polymers have shown promising results in early damage detection through mechanically induced fluorescence. A spring-bead based network model, which bridges nanoscale information to higher length scales, has been developed to model this material system. The material is partitioned into discrete mass beads which are linked using linear springs at the microscale. A series of MD simulations were performed to define the spring stiffness in the statistical network model. By integrating multiple spring-bead models a network model has been developed to represent the material properties at the mesoscale. The model captures the statistical distribution of crosslinking degree of the polymer to represent the heterogeneous material properties at the microscale. The developed multiscale methodology is computationally efficient and provides a possible means to bridge multiple length scales (from 10 nm in MD simulation to 10 mm in FE model) without significant loss of accuracy. Parametric studies have been conducted to investigate the influence of the crosslinking degree on the material behavior. The developed methodology has been used to evaluate damage evolution in the self-sensing polymer.

A hybrid molecular dynamics (MD) simulation framework is developed to emulate mechanochemical reaction of mechanophores in epoxy-based nanocomposites. Two different force fields, a classical force field and a bond order based force field are hybridized to mimic the experimental processes from specimen preparation to mechanical loading test. Ultra-violet photodimerization for mechanophore synthesis and epoxy curing for thermoset polymer generation are successfully simulated by developing a numerical covalent bond generation method using the classical force field within the framework. Mechanical loading tests to activate mechanophores are also virtually conducted by deforming the volume of a simulation unit cell. The unit cell deformation leads to covalent bond elongation and subsequent bond breakage, which is captured using the bond order based force field. The outcome of the virtual loading test is used for local work analysis, which enables a quantitative study of mechanophore activation. Through the local work analysis, the onset and evolution of mechanophore activation indicating damage initiation and propagation are estimated; ultimately, the mechanophore sensitivity to external stress is evaluated. The virtual loading tests also provide accurate estimations of mechanical properties such as elastic, shear, bulk modulus, yield strain/strength, and Poisson’s ratio of the system. Experimental studies are performed in conjunction with the simulation work to validate the hybrid MD simulation framework. Less than 2% error in estimations of glass transition temperature (Tg) is observed with experimentally measured Tgs by use of differential scanning calorimetry. Virtual loading tests successfully reproduce the stress-strain curve capturing the effect of mechanophore inclusion on mechanical properties of epoxy polymer; comparable changes in Young’s modulus and yield strength are observed in experiments and simulations. Early damage signal detection, which is identified in experiments by observing increased intensity before the yield strain, is captured in simulations by showing that the critical strain representing the onset of the mechanophore activation occurs before the estimated yield strain. It is anticipated that the experimentally validated hybrid MD framework presented in this dissertation will provide a low-cost alternative to additional experiments that are required for optimizing material design parameters to improve damage sensing capability and mechanical properties.

In addition to the study of mechanochemical reaction analysis, an atomistic model of interphase in carbon fiber reinforced composites is developed. Physical entanglement between semi-crystalline carbon fiber surface and polymer matrix is captured by introducing voids in multiple graphene layers, which allow polymer matrix to intertwine with graphene layers. The hybrid MD framework is used with some modifications to estimate interphase properties that include the effect of the physical entanglement. The results are compared with existing carbon fiber surface models that assume that carbon fiber has a crystalline structure and hence are unable to capture the physical entanglement. Results indicate that the current model shows larger stress gradients across the material interphase. These large stress gradients increase the viscoplasticity and damage effects at the interphase. The results are important for improved prediction of the nonlinear response and damage evolution in composite materials.

This dissertation will investigate two of the most promising high-capacity anode

materials for lithium-based batteries: silicon (Si) and metal lithium (Li). It will focus on

studying the mechanical behaviors of the two materials during charge and discharge and

understanding how these mechanical behaviors may affect their electrochemical

performance.

In the first part, amorphous Si anode will be studied. Despite many existing studies

on silicon (Si) anodes for lithium ion batteries (LIBs), many essential questions still exist

on compound formation, composition, and properties. Here it is shown that some

previously accepted findings do not truthfully reflect the actual lithiation mechanisms in

realistic battery configurations. Furthermore the correlation between structure and

mechanical properties in these materials has not been properly established. Here, a rigorous

and thorough study is performed to comprehensively understand the electrochemical

reaction mechanisms of amorphous-Si (a-Si) in a realistic LIB configuration. In-depth

microstructural characterization was performed and correlations were established between

Li-Si composition, volumetric expansion, and modulus/hardness. It is found that the

lithiation process of a-Si in a real battery setup is a single-phase reaction rather than the

accepted two-phase reaction obtained from in-situ TEM experiments. The findings in this

dissertation establish a reference to quantitatively explain many key metrics for lithiated a

Si as anodes in real LIBs, and can be used to rationally design a-Si based high-performance

LIBs guided by high-fidelity modeling and simulations.

In the second part, Li metal anode will be investigated. Problems related to dendrite

growth on lithium metal anodes such as capacity loss and short circuit present major

barriers to the next-generation high-energy-density batteries. The development of

successful mitigation strategies is impeded by the incomplete understanding of the Li

dendrite growth mechanisms. Here the enabling role of plating residual stress in dendrite

initiation through novel experiments of Li electrodeposition on soft substrates is confirmed,

and the observations is explained with a stress-driven dendrite growth model. Dendrite

growth is mitigated on such soft substrates through surface-wrinkling-induced stress

relaxation in deposited Li film. It is demonstrated that this new dendrite mitigation

mechanism can be utilized synergistically with other existing approaches in the form of

three-dimensional (3D) soft scaffolds for Li plating, which achieves superior coulombic

efficiency over conventional hard copper current collectors under large current density.

Energy harvesting from ambient is important to configuring Wireless Sensor Networks (WSN) for environmental data collecting. In this work, highly flexible thermoelectric generators (TEGs) have been studied and fabricated to supply power to the wireless sensor notes used for data collecting in hot spring environment. The fabricated flexible TEGs can be easily deployed on the uneven surface of heated rocks at the rim of hot springs. By employing the temperature gradient between the hot rock surface and the air, these TEGs can generate power to extend the battery lifetime of the sensor notes and therefore reduce multiple batteries changes where the environment is usually harsh in hot springs. Also, they show great promise for self-powered wireless sensor notes. Traditional thermoelectric material bismuth telluride (Bi2Te3) and advanced MEMS (Microelectromechanical systems) thin film techniques were used for the fabrication. Test results show that when a flexible TEG array with an area of 3.4cm2 was placed on the hot plate surface of 80°C in the air under room temperature, it had an open circuit voltage output of 17.6mV and a short circuit current output of 0.53mA. The generated power was approximately 7mW/m2.

On the other hand, high pressure, temperatures that can reach boiling, and the pH of different hot springs ranging from <2 to >9 make hot spring ecosystem a unique environment that is difficult to study. WSN allows many scientific studies in harsh environments that are not feasible with traditional instrumentation. However, wireless pH sensing for long time in situ data collection is still challenging for two reasons. First, the existing commercial-off-the-shelf pH meters are frequent calibration dependent; second, biofouling causes significant measurement error and drift. In this work, 2-dimentional graphene pH sensors were studied and calibration free graphene pH sensor prototypes were fabricated. Test result shows the resistance of the fabricated device changes linearly with the pH values (in the range of 3-11) in the surrounding liquid environment. Field tests show graphene layer greatly prevented the microbial fouling. Therefore, graphene pH sensors are promising candidates that can be effectively used for wireless pH sensing in exploration of hot spring ecosystems.

Origami and kirigami, the technique of generating three-dimensional (3D) structures from two-dimensional (2D) flat sheets, are now more and more involved in scientific and engineering fields. Therefore, the development of tools for their theoretical analysis becomes more and more important. Since much effort was paid on calculations based on pure mathematical consideration and only limited effort has been paid to include mechanical properties, the goal of my research is developing a method to analyze the mechanical behavior of origami and kirigami based structures. Mechanical characteristics, including nonlocal effect and fracture of the structures, as well as elasticity and plasticity of materials are studied. For calculation of relative simple structures and building of structures’ constitutive relations, analytical approaches were used. For more complex structures, finite element analysis (FEA), which is commonly applied as a numerical method for the analysis of solid structures, was utilized. The general study approach is not necessarily related to characteristic size of model. I believe the scale-independent method described here will pave a new way to understand the mechanical response of a variety of origami and kirigami based structures under given mechanical loading.