The microwave, optical, and electro-optic properties of epitaxial barium titanate thin films grown on (100) MgO substrates and photonic crystal electro-optic modulators fabricated on these films were investigated to demonstrate the applicability of these devices for telecommunication and data networks. The electrical and electro-optical properties were characterized up to modulation...
Worldwide, governments are beginning to take action to reduce anthropogenic CO2 emissions in order to mitigate the extent of global climate change. The largest fraction of global CO2 emission comes from electrical power generation, which is rapidly being converted to wind and solar installations. The intermittent nature of renewable resources...
Organic photovoltaic (OPV) solar cells aim to provide efficient, flexible and lightweight photovoltaics (PV) with simple processing and low-cost. Advances in device optimization, structural and molecular design, as well as mechanistic understanding have helped increase device efficiency and performance. Within the framework of active layer optimization, systematically improving bulk heterojunction...
Growing energy and climate concerns in the United States and across the world demand improvements in energy efficiency, conservation, and renewability. Solid oxide fuel cells (SOFCs) are highly efficient devices that electrochemically convert the chemical energy of a fuel to electricity. These devices can operate on natural gas as a...
Nano-structured mixed ionic and electronic conducting (MIEC) materials have garnered intense interest in electrode development for solid oxide fuel cells due to their high surface areas which allow for effective catalytic activity and low polarization resistances. In particular, composite solid oxide fuel cell (SOFC) cathodes consisting of ionic conducting scaffolds...
The impacts of many important technologies are limited by the availability of better-performing materials. One factor limiting the ability of engineers to develop better materials is the speed at which they can search through possible formulations and processing schemes. Recently, machine learning algorithms have emerged as a possible route to...
Increasing energy demand due to rapid growth in population and industrialization along with environmental crisis has led to the search for cheap, environmentally friendly, and nontoxic methods for generation of energy. However, most alternative energy sources such as photovoltaic, biofuels, hydraulic power, wind power, and geothermal energy, are characterized by...
Metal and bimetallic nanoparticles are of interest and are widely used in various applications because of their unique optical, electronic, and catalytic properties, which differ from those of their bulk counterparts. Better understanding of the thermodynamic and kinetic properties of nanoparticles and their underlying growth mechanisms can serve as a...
Significant deviations in the glass transition temperature (Tg) of nanoconfined polymer films from the bulk have been studied for over twenty years with the focus on high molecular weight (MW), linear polymers. This thesis explores low MW polymers, which represent an important class of materials widely used as coatings, detergents,...
Accurate thermodynamic databases are the foundation of predictive microstructure and property models. An initial assessment of the commercially available Thermo-Calc TCAL2 database and the proprietary aluminum database of QuesTek demonstrated a large degree of deviation with respect to equilibrium precipitate phase prediction in the compositional region of interest when compared...
In today's rapidly changing world, there is constant demand for the development of new, high performance materials. Fire resistant steels can provide greater safety in the event of a building fire, creep resistant stainless steels can allow for higher power plant efficiency, and cobalt based superalloys have potential for use...
Graphene offers promising opportunities for applications in printed and flexible electronic devices due to its high electrical and thermal conductivity, mechanical flexibility and strength, and chemical and environmental stability. However, scalable production and processing of graphene presents a critical technological challenge preventing the application of graphene for flexible electronic interconnects,...
The transport properties of mayenite-based materials, Ca12Al14O33, were investigated. Systems studied included H-doped/ UV-irradiated Ca12Al14O33, Ca(12-x)MgxAl14O33 (x = 0.1, 0.3, 0.5, 0.8, 1) and Ca12Al(14-x)SixO(33+x/2) (x = 1, 2, 3, 4). The as-prepared Ca12Al14O33 exhibited a room temperature electronic conductivity on the order of 10^-10 S/cm, and a high temperature...
The electronic transport and magnetoresistive properties of the ferromagnetic semiconductor In1-xMnxAs were investigated in order to determine the nature of the transport and ferromagnetism in the films. p-InMnAs/n-InAs and metal/oxide/InMnAs heterojunctions were fabricated and characterized to elucidate the transport and magnetoresistance mechanisms at these technologically important interfaces.
The electronic transport...
Biomorphic silicon carbide (bioSiC) is a novel porous ceramic material derived directly from wood precursors. This material is fabricated by pyrolysis of a natural wood precursor in an inert atmosphere leaving an amorphous carbon scaffold. The amorphous carbon is infiltrated with molten Si in vacuum at elevated temperature, which reacts...
Solid oxide fuel cells (SOFCs), renowned for their high electrical generation efficiency with low pollutant production, are promising for reducing global energy and environmental concerns. However, there are major barriers for SOFC commercialization. A primary challenge is reducing the capital cost of SOFC power plants to levels that can compete...
Fundamental investigations on the origins of friction at the nanoscale were carried out using both theoretical and experimental approaches. A model was developed that analytically solves for friction by the motion of dislocations at atomically flat crystalline interfaces. It combines known concepts from dislocation drag, grain boundary theory, and contact...
The optical and magneto-optical properties of the ferromagnetic semiconductors, InMnAs and its alloy InMnAsP were investigated to determine the band structure and nature of the ferromagnetism in these materials. Alloys were grown by metal-organic vapor phase epitaxy. Infrared absorption of InMnAs was investigated to determine the presence and properties of...
Ceramic matrix composites are known for their low density, high strength and high stiffness, but lower fracture toughness compared to metal matrix composites. The addition of a reinforcing agent within the matrix can increase the toughness of the composite via many strain energy absorption mechanisms such as plastic deformation. This...
Using ab initio calculations, we discovered a quasi two-dimensional copper–bismuth nano sheet, which we call cubine. According to our predictions, single layers of cubine can be isolated from the recently reported high-pressure CuBi bulk material at an extremely low energetic cost, comparable to values to separate single layers of graphene...
Supramolecular chemistry has proven to be an effective strategy for bottom-up fabrication of monodisperse, functional nanostructures. However, most applications require these nanostructures to be spatially or orientationally ordered. This thesis investigates patterning and spatial confinement as tools for controlling order in self-assembling systems.
We first look to improve the ordering...
Polymers and polyelectrolytes are ideal tools for the development of novel self-assembled materials. The ability to control the length-scales of self-assembly, and thus the properties, for soft materials lies in the understanding and subsequent manipulation of competing intermolecular interactions, such as hydrophobicity, hydrogen bonding, van der Waals, electrostatics. In this...
Novel self-healing alloy composites have been designed to address the need for self-repairable high-strength structural materials. A systems-based materials design approach using computational design tools was used to design a multifunctional biomimetic composite that can repair structural damage. The self-healing composite consists of a controlled-melting alloy matrix reinforced by thermodynamically...
In high power density transmission systems, Ni-Co secondary hardening steels have shown great potential for next-generation gear applications due to their excellent strength, toughness and superior fatigue performance.
Study of residual stress generation and evolution in Ferrium C61 and C67 gear steels revealed that shot peening and laser peening processes...
Over the past two decades photonic crystals (PhCs) have emerged as a promising new class of materials which offers unprecedented control of light in materials. Recently, atomic layer deposition (ALD) has been shown to be a powerful tool for the infiltration of 3D templates with dielectric or semiconducting materials, which...
Oxide surface structures play a key role in many technological processes, including catalysis, thin film growth, and layered structures, and a thorough understanding of surface structures and surface structure dynamics is required in order to better engineer materials systems for these processes. This research works towards understanding these fundamental principles...
In this work, the processing of the superconductor MgB<sub>2</sub> was studied to create a fundamental scientific background for the production of superconducting composite wires. The synthesis of MgB<sub>2</sub> from Mg and B powders was investigated in situ to determine reaction rates and kinetic parameters for the application of powder-in-tube technology...
Gradient copolymers are novel materials that possess a gradual variation in composition along the chain, thereby forming an intermediate structure between random and block copolymers. As such, they are a model system to investigate the effect of molecular structure on fundamental properties of copolymers and may be useful in many...
Because soft materials, particularly polymer gels, are playing a greater role in industrial and biotechnological applications today, the exploration of their mechanical behavior over a range of deformations is becoming more relevant in our daily lives. Understanding these properties is therefore necessary as a means to predict their response for...
In this dissertation, the Tg behavior of nanoconfined polymer films and 1-dimensional (1-D) patterned polymer nanostructures was studied. Using a novel fluorescence method, a reduction in Tg was observed upon confinement in PS films supported on silica, where free-surface (polymer-air interface) effects are dominant in modifying Tg. In contrast, Tg...
This thesis examines the effects of micro-alloying additions to Al-Sc alloys on the microstructure, coarsening resistance and creep properties. The overarching goal of this research is to develop castable, creep-resistant aluminum alloys which can be used at temperatures in excess of 300?C. Successful high-temperature application of aluminum based alloys offers...
A series of investigations was undertaken to explore the processing and properties of porous titanium with 6 wt% Al and 4 wt% vanadium (Ti-6Al-4V) and an equiatomic nickel-titanium alloy (NiTi). In this study, porous materials were created in the solid state by entrapping argon in a powder compact, and subsequently...
Aluminum alloys strengthened with coherent (L1<sub>2</sub>), nanosize Al<sub>3</sub>Sc precipitates may be used as structural materials at elevated temperatures. They are creep resistant at 300°C and exhibit a threshold stress, below which creep is not measurable. Introducing ternary alloying additions, such as rare-earth elements (RE=Y, Dy, Er), that segregate within Al<sub>3</sub>Sc...
Dimensionally constrained material systems are at the forefront of current materials research because of their novel and often enhanced physical, chemical and biological properties. The dimensionality effects are pervasive through different classes of materials including ceramics, metals and polymers. Often times dimensionality effects are manifested as internal structure variations in...
For bone regeneration, there is need for biodegradable, synthetic scaffolds that direct the formation of <em>de novo</em> mineralized tissue. Orthopaedic implants additionally require mechanical function. The work described herein attempts to address both of these needs. The general strategy involves integrating molecularly designed tissue engineering scaffolds with porous metallic foams...
The work presented in this dissertation focuses on ceramic anode materials for solid oxide fuel cells (SOFCs). The primary goal was to characterize the anode and relate the electrochemical behavior to the microstructure. The anode that was most extensively studied in this work was a composite of Gd0.10Ce0.90O1.95 (GDC) and...
The kinetics of nanoscale Cu-rich precipitates of multicomponent concentrated steels has been investigated utilizing primarily APT and supplemented with a synchrotron radiation experiment, first-principles calculations, Thermo-Calc study, and CTEM (at the longest aging time). Results on mechanical properties and microstructure at a greater length scale are also presented. The studied...
This dissertation demonstrates how self-assembly can direct nanoscale ordering and optimize electronic properties of organic semiconductors, as well as organic-inorganic hybrids. In excitonic solar cells, controlling the ordering and interfaces between electron-transporting (n-type) and hole-transporting (p-type) domains is crucial. In addressing this challenge, hybrid nanostructures were designed by mineralization of...
A novel cryogenic variable temperature UHV STM has been constructed and utilized to investigate the dynamical behavior of isolated organic molecules covalently bound to silicon surfaces.
The microscope can be operated from 8-300 K, and exhibits extremely low drift rates. A new design has been implemented for the rails (used...
Two main topics are addressed in this dissertation: (1) adhesion in hydrogels; (2) interfacial interactions between model glassy polymers. A self-assembly technique for the formation of hydrogels from acrylic triblock copolymer solutions was developed, based on vapor phase solvent exchange. Structure formation in the gels was characterized by small angle...
Metal nanoparticles in polymeric matrices are of particular scientific interest due to their useful ability to self-assemble into complex nanocomposites. Recent examples involve using ultrathin diblock copolymers coupled with metal nanoparticles in the fabrication of novel electronic, magnetic and photonic devices. As this ordering process takes place far from equilibrium...
The current trend of ceramic nanotechnology has motivated an ever-increasing need to achieve exquisite control over size, shape, and spatial confinement for functional oxide architectures, in an equivalent manner demonstrated for semiconductors. However, the unique nature of ceramics has posed major challenges for most traditional nanofabrication technologies, putting the development...
The use of composites is increasing as they afford scientists and engineers the ability to combine the advantageous properties of each constituent phase, e.g. metal ductility and ceramic stiffness. With respect to materials design, biomimetics is garnering increasing attention due to the complex, yet efficient, natural microstructures. One such biomimetic,...
The measurement of weak adhesive energies has previously been difficult to obtain. To measure these energies, I designed a technique that uses the combined sensitivities of both a quartz crystal resonator and the inflation of an elastomeric polymer membrane. The surfaces of the quartz crystal and/or the membrane are modified...
Liquid metal melt-lubrication of high-power and high-speed sliding electrical contacts improves electrical current collection and reduces friction. However, armature material loss may cause transition to arcing or plasma contact. Boundary lubrication of the sliding contact with low melting-point alloys can provide comparable improvement in current collection at reduced temperatures. Bismuth,...
In recent years, research has expanded the uses of triblock copolymer gels to a wide variety of applications including everything from ceramics processing to regenerative medicine and drug delivery. The research presented in this dissertation focuses on a physically crosslinked, block copolymers gel system in a selective solvent. This system...
Motivated by performance requirements of future medical stent applications, experimental research addresses the design of novel TiNi-based, superelastic shape-memory alloys employing nanoscale precipitation strengthening to minimize accommodation slip for cyclic stability and to increase output stress capability for smaller devices. Using a thermodynamic database describing the B2 and L21 phases...
Increasing interest in long-life bone implants with reduced mechanical properties reducing the stress-shielding effect and a structure mimicking bone porous architecture has encouraged study and development of fabrication methods for porous NiTi. The main objective of this work was to advance these goals by developing new processing procedures for porous...
In this work, electron beam induced current (EBIC) and scanning photocurrent microscopy (SPCM) were used to quantitatively investigate the electronic properties of silicon nanowire devices. For the first time, it was shown that minority carrier diffusion lengths in phosphorous-doped silicon nanowires are significantly reduced from their bulk values because of...
A multicomponent bimodal poly(vinyl acetate) (PVAc) polymer composite has been scientifically designed to increase biaxial plastic flow stabilization for the achievement of large biaxial deformations. For this, a systems-based approach was used for the computational materials design of a high performance bubblegum whose mean in-vivo bubble diameter exceeds that of...