In this thesis, I utilize first principles density functional theory (DFT) based calculations to investigate the structure and electronic properties including charge transfer behaviors and work function of two types of materials: pentacene based organic semiconductors and ZnO transparent conducting oxides, with an aim to search for high mobility n-type organic semiconductors and fine tuning work functions of ZnO through surface modifications. Based on DFT calculations of numerous structure combinations, I proposed a pentacene and perfluoro-pentacene alternating hybrid structures as a new type of n-type semiconductor. Based on the DFT calculations and Marcus charge transfer theory analysis, the new structure has high charge mobility and can be a promising new n-type organic semiconductor material. DFT calculations have been used to systematically investigate the effect of surface organic absorbate and surface defects on the work function of ZnO. It was found that increasing surface coverage of organic groups and decreasing surface defects lead to decrease of work functions, in excellent agreement with experimental results. First principles based calculations thus can greatly contribute to the investigating and designing of new electronic materials.

Mechanics of bone is widely studied and researched, mainly for the study of fracture. This has been done mostly on a macro scale. In this work hierarchical nature of bone has been explored to investigate bone mechanics in more detail. Flexural test were done to classify the bones according to their strength and deflection. Raman spectroscopy analysis was done to map the mineralization, collagen crosslinking changes across the thickness of the bone. Nanoindentation was done to map indentation hardness and indentation modulus across femoral cortex of the bone. The results indicate that the composition of the bone changes across the thickness of the femoral cortex. The hypothesis is confirmed as increase in mineralization, carbonate to phosphate ratio and collagen crosslinking shows the effect as increased indentation hardness and modulus and decreased deflection.

Lack of crystalline order and microstructural features such as grain/grain-boundary in metallic glasses results in a suite of remarkable attributes including very high strength, close to theoretical elasticity, high corrosion and wear resistance, and soft magnetic properties. In particular, low coercivity and high permeability of iron and cobalt based metallic glass compositions could potentially lead to extensive commercial use as magnetic heads, transformer cores, circuits and magnetic shields. In the current study, few metallic glass compositions were synthesized by systematically varying the iron and cobalt content. Thermal analysis was done and included the measurement of glass transition temperature, crystallization temperature, and the enthalpies of relaxation and crystallization. Magnetic properties of the alloys were determined including saturation magnetization, coercivity, and Curie temperature. The coercivity was found to decrease and the saturation magnetization was found to increase with the increase in iron content. The trend in thermal stability, thermodynamic properties, and magnetic properties was explained by atomic interactions between the ferromagnetic metals and the metalloids atoms in the amorphous alloys. Mechanical behavior of iron based metallic glasses was evaluated in bulk form as well as in the form of coatings. Iron based amorphous powder was subjected to high power mechanical milling and …

The current study focuses on phase stability and evolution in the titanium-zinc titanium-copper and titanium-antimony systems. The study utilized the Laser Engineering Net Shaping (LENS™) processing technique to deposit compositionally graded samples of three binary system in order to allow the assessment of phase stability and evolution as a function of composition and temperature the material is subjected to. Through LENS™ processing it was possible to create graded samples from Ti-xSb (up to 13wt%) and Ti-xCu (up to 16wt%). The LENS™ deposited gradient were solutionized, and step quenched to specific aging temperature, and the resulting microstructures and phase were characterized utilizing XRD, EDS, SEM, FIB and TEM. The Ti-Zn system proved incapable of being LENS™ deposited due to the low vaporization temperature of Zn; however, a novel processing approach was developed to drip liquid Zn onto Ti powder at temperatures above β transus temperature of Ti (882 ◦C) and below the vaporization temperature of Zn (907 ◦C). The product of this processing technique was characterized in a similar way as the graded LENS™ depositions. From measurements performed on Ti-Sb it seems that Sb could be a potential α stabilizer in Ti due to the presence of a mostly homogeneous α …

Ultra-fine grained materials with sub-micrometer grain size exhibit superior mechanical properties when compared with conventional fine-grained material as well as coarse-grained materials. Severe plastic deformation (SPD) techniques have been shown to be an effective way to modify the microstructure in order to improve the mechanical properties of the material. Crystalline materials require dislocations to accommodate plastic strain gradients and maintain lattice continuity. The lattice curvature exists due to the net dislocation that left behind in material during deformation. The characterization of such defects is important to understand deformation accumulation and the resulting mechanical properties of such materials. However, traditional techniques are limited. For example, the spatial resolution of EBSD is insufficient to study materials processed via SPD, while high dislocation densities make interpretations difficult using conventional diffraction contrast techniques in the TEM. A new technique, precession electron diffraction (PED) has gained recognition in the TEM community to solve the local crystallography, including both phase and orientation, of nanocrystalline structures under quasi-kinematical conditions. With the assistant of precession electron diffraction coupled ASTARÔ, the structure evolution of equal channel angular pressing processed commercial pure titanium is studied; this technique is also extended to two-phase titanium alloy (Ti-5553) to investigate the existence of …

Conversion material electrodes such as FeF2 possess the potential to deliver transformative improvements in lithium ion battery performance because they permit a reversible change of more than one Li-ion per 3d metal cation. They outperform current state of the art intercalation cathodes such as LiCoO2, which have volumetric and gravimetric energy densities that are intrinsically limited by single electron transfer. Current studies focus on composite electrodes that are formed by mixing with carbon (FeF2-C), wherein the carbon is expected to act as a binder to support the matrix and facilitate electronic conduction. These binders complicate the understanding of the electrode-electrolyte interface (SEI) passivation layer growth, of Li agglomeration, of ion and electron transport, and of the basic phase transformation processes under electrochemical cycling. This research uses thin-films as a model platform for obtaining basic understanding to the structural and chemical foundations of the phase conversion processes. Thin film cathodes are free of the binders used in nanocomposite structures and may potentially provide direct basic insight to the evolution of the SEI passivation layer, electron and ion transport, and the electrochemical behavior of true complex phases. The present work consisted of three main tasks (1) Development of optimized processes to deposit …

Widespread use of organic light emitting diodes (OLEDs) in solid state lighting and display technologies require efficiency and lifetime improvements, as well as cost reductions, inclusive of the transparent conducting oxide (TCO). Indium tin oxide (ITO) is the standard TCO anode in OLEDs, but indium is expensive and the Earth's reserve of this element is limited. Zinc oxide (ZnO) and its variants such as aluminum-doped ZnO (AZO) exhibit comparable electrical conductivity and transmissivity to ITO, and are of interest for TCO applications. However, the workfunction of ZnO and AZO is smaller compared to ITO. The smaller workfunction of AZO results in a higher hole injection barrier at the anode/organic interface, and methods of tuning its workfunction are required. This dissertation tested the hypothesis that workfunction tuning of AZO films could be achieved by surface modification with electronegative oxygen and fluorine plasmas, or, via use of nanoscale transition metal oxide layers (MoOx, VOx and WOx). Extensive UPS, XPS and optical spectroscopy studies indicate that O2 and CFx plasma treatment results in an electronegative surface, surface charge redistribution, and a surface dipole moment which reinforces the original surface dipole leading to workfunction increases. Donor-like gap states associated with partially occupied d-bands due …

ZnO and ZnO-TiO2 ceramics have intriguing electronic and mechanical properties and find applications in many fields. Many of these properties and applications rely on the understanding of defects and defect processes in these oxides as these defects control the electronic, catalytic and mechanical behaviors. The goal of this dissertation is to systematically study the defects and defects behaviors in Wurtzite ZnO and Ilmenite ZnTiO3 by using first principles calculations and classical simulations employing empirical potentials. Firstly, the behavior of intrinsic and extrinsic point defects in ZnO and ZnTiO3 ceramics were investigated. Secondly, the effect of different surface absorbents and surface defects on the workfunction of ZnO were studied using DFT calculations. The results show that increasing the surface coverage of hydrocarbons decreased the workfunction. Lastly, the stacking fault behaviors on ilmenite ZnTiO3 were investigated by calculating the Generalized Stacking Fault (GSF) energies using density functional theory based first principles calculations and classical calculations employing effective partial charge inter-atomic potentials. The gamma-surfaces of two low energy surfaces, (110) and (104), of ZnTiO3 were fully mapped and, together with other analysis such as ideal shear stress calculations.

β-Ti alloys are widely used in airframe and biomedical applications due to their high ductility, high hardenability, and low elastic modulus. The phase transformations in β-Ti alloys are rather complex due to formation of metastable phases during various thermo-mechanical treatments. One such critical metastable phase, the hexagonal omega (ω) phase, can form in β-Ti alloys under quenching from the high temperature β phase and/or isothermal aging at intermediate temperature. Despite a substantial amount of reported works on the ω phase, there are several critical issues related to the ω formation need to be resolved, e.g. role of alloying elements and oxygen content. Therefore, this dissertation has attempted to provide insights into ω transformation in low misfit (Ti-Mo) and high misfit (Ti-V) binary systems as well as multicomponent (Ti-Nb-Zr-Ta) alloys. The evolution of ω structure, morphology and composition from the early stage (β-solution+quenched) to later stages after prolonged aging are systematically investigated by coupling transmission electron microscopy (TEM), atom probe tomography (APT) and high-energy synchrotron X-ray diffraction techniques. The influence of aging temperature and duration on characteristic of ω phase in Ti-Mo, and Ti-V alloys is addressed in details. It is found that compositional changes during aging can alter the structure, …

The widespread use of electronics in more avenues of consumer use is increasing. Applications range from medical instrumentation that directly can affect someone's life, down hole sensors for oil and gas, aerospace, aeronautics, and automotive electronics. The increased power density and harsh environment makes the reliability of the packaging a vital part of the reliability of the device. The increased importance of analog devices in these applications, their high voltage and high temperature resilience is resulting in challenges that have not been dealt with before. In particular packaging where insulative properties are vital use polymer resins modified by ceramic fillers. The distinct dielectric properties of the resin and the filler result in charge storage and release of the polarization currents in the composite that have had unpredictable consequences on reliability. The objective of this effort is therefore to investigate a technique that can be used to measure the polarization in filled polymer resins and evaluate reliable molding compounds. A valuable approach to measure polarization in polymers where charge release is tied to the glass transition in the polymer is referred to as thermally stimulated depolarization current (TSDC) technique. In this dissertation a new TSDC measurement system was designed and fabricated. …

The recent advancements in electronics and the advents of small scaled instruments has increased the attachment of life and functionality of devices to electrical power sources but at the same time granted the engineers and companies the ability to use smaller sources of power and batteries. Therefore, many scientists have tried to come up with new solutions for a power alternatives. Piezoelectric is a promising material which can readily produce continuous electric power from mechanical inputs. However, their power output is dependent upon several factors such as, system natural frequency, their position in the system, the direction of vibration and many other internal and external factors. In this research the working bandwidth of the system is increased through utilizing of two different piezoelectric beam in different directions. The dependency of output power with respect to rotation angle and also the frequency shift due to the rotation angle is studied.

The physical characteristics (i.e., nanostructure and stiffness) of the extracellular matrix where cells reside have been shown to profoundly affect numerous cellular events in vivo and also been employed to modulate cell behavior in vitro, yet how these physical cues regulate cell behavior is still elusive. Therefore, we engineered a variety of nanotopographies with different shapes and dimensions, and investigated how the nanotopographical cue, through focal adhesions-cytoskeleton-nucleus pathway, affected cell phenotype and function. We further designed and fabricated well-defined substrates which had either identical biochemical cue (adhesive ligand presentation) but different nanotopographical cues or identical nanotopography but different biochemical cues, and dissected the roles of these cues in cell modulation. In addition, we revealed that the human mesenchymal stem cells (hMSCs) could obtain nanotopographical memory from the past culture environment, and the nanotopographical memory influenced the future fate decision of the hMSCs. Moreover, we evaluated the effects of substrate nanotopographical and stiffness cues on the fibrogenesis of human lung fibroblasts in response to carbon nanotubes and highlighted the significance of these physical cues in the development of physiologically relevant in vitro models for nanotoxicological study. The mechanistic understanding of the physical regulation of cell behaviors will provide important insight into …

Structural material fatigue is a leading cause of failure and has motivated fatigue-resistant design to eliminate risks to human lives. Intrinsic microstructural features alter fatigue deformation mechanisms so profoundly that, essentially, fatigue properties of structural materials become deviant. With this in mind, we initiated this project to investigate the microstructural effect on fatigue behavior of potential structural high entropy alloys. With a better understanding of the effect of microstructure features on fatigue properties, the ultimate goal was to engineer the microstructure to enhance the fatigue life of structural materials. The effects of two major deformation mechanisms presented here are twinning-induced fatigue crack retardation, and transformation-induced fatigue crack retardation. The fundamental principle of both mechanisms is to delay the fatigue crack propagation rate by altering the work hardening ability locally within the crack plastic zone. In ultrafine grained triplex Al0.3CoCrFeNi, nano-sized deformation twins were observed during cyclic loading in FCC matrix due to low stacking fault energy (SFE). The work-hardening ability of the material near the crack was sustained with the formation of twins according to Considere's criteria. Further, due to the ultrafine-grained (UFG) nature of the material, fatigue runout stress was enhanced. In a coarse-grained, dual-phase high entropy alloy, persistent …