Metallic glasses possess attractive properties, such as high strength, good corrosion resistance, and superior soft magnetic performance. They also serve as precursors for synthesizing nanocrystalline materials. In addition, a new class of composites having crystalline phases embedded in amorphous matrix is evolving based on selective crystallization of metallic glasses. Therefore, crystallization of metallic glasses and its effects on properties has been a subject of interest. Previous investigations from our research group related to laser assisted crystallization of Fe-Si-B metallic glass (an excellent soft magnetic material by itself) showed a further improvement in soft magnetic performance. However, a fundamental understanding of crystallization and mechanical performance of laser treated metallic glass was essential from application point of view. In light of this, the current work employed an integrated experimental and computational approach to understand crystallization and its effects on tensile behavior of laser treated Fe-Si-B metallic glass. The time temperature cycles during laser treatments were predicted using a finite element thermal model. Structural changes in laser treated Fe-Si-B metallic glass including crystallization and phase evolution were investigated with the aid of X-ray diffraction, differential scanning calorimetry, resistivity measurements, and transmission electron microscopy. The mechanical behavior was evaluated by uniaxial tensile tests with …

Shape memory alloys (SMAs) exhibit the ability to absorb large dynamic loads and, therefore, are excellent candidates for structural components where impact loading is expected. Compared to the large amount of research on the shape memory effect and/or pseudoelasticity of polycrystalline SMAs under quasi-static loading conditions, studies on dynamic loading are limited. Experimental research shows an apparent difference between the quasi-static and high strain rate deformation of SMAs. Research reveals that the martensitic phase transformation is strain rate sensitive. The mechanism for the martensitic phase transformation in SMAs during high strain rate deformation is still unclear. Many of the existing high strain rate models assume that the latent heat generated during deformation contributes to the change in the stress-strain behavior during dynamic loading, which is insufficient to explain the large stress observed during phase transformation under high strain rate deformation. Meanwhile, the relationship between the phase front velocity and strain rate has been studied. In this dissertation, a new resistance to phase transformation during high strain rate deformation is discussed and the relationship between the driving force for phase transformation and phase front velocity is established. With consideration of the newly defined resistance to phase transformation, a new model for …

Phosphorescent organic light emitting diodes (PHOLEDs) based on efficient electrophosphorescent dopant, platinum(II)-pyridyltriazolate complex, bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) have been studied and improved with respect to power efficiency, external efficiency, chromacity and efficiency roll-off. By studying the electrical and optical behavior of the doped devices and functionality of the various constituent layers, devices with a maximum EQE of 20.8±0.2 % and power efficiency of 45.1±0.9 lm/W (77lm/W with luminaries) have been engineered. This improvement compares to devices whose emission initially could only be detected by a photomultiplier tube in a darkened environment. These devices consisted of a 65 % bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) doped into 4,4'-bis(carbazol-9-yl)triphenylamine (CBP) an EML layer, a hole transporting layer/electron blocker of 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), an electron transport layer of 1,3,5-tris(phenyl-2-benzimidazolyl)-benzene (TPBI), and a LiF/Al cathode. These devices show the acceptable range for warm white light quadrants and qualify to be called "warm white" even w/o adding another emissive layer. Dual EML devices composed of neat Pt(ptp)2 films emitting orange and CBP: Pt(ptp)2 film emitting blue-green produced a color rendering index (CRI) of 59 and color coordinates (CIE) of (0.47,0.49) at 1000Cd/m² with power efficiency of 12.6±0.2 lm/W and EQE of 10.8±0.2 %. Devices with two blue fluorescent emission layers as singlet …

Transient electroluminescence (EL) was used to measure the onset of emission delay in OLEDs based on transition metal, phosphorescent bis[3,5-bis(2-pyridyl)-1,2,4-triazolato] platinum(ΙΙ) and rare earth, phosphorescent Eu(hfa)3 with 4'-(p-tolyl)-2,2":6',2" terpyridine (ttrpy) doped into 4,4'-bis(carbazol-9-yl) triphenylamine (CBP), from which the carrier mobility was determined. For the Pt(ptp)2 doped CBP films in OLEDs with the structure: ITO/NPB (40nm)/mcp (10nm)/65% Pt(ptp)2:CBP (25nm)/TPBI (30nm)/Mg:Ag (100nm), where NPB=N, N'-bis(1-naphthyl)-N-N'-biphenyl-1, 1'-biphenyl-4, MCP= N, N'-dicarbazolyl-3,5-benzene, TPBI=1,3,5-tris(phenyl-2-benzimidazolyl)-benzene, delayed recombination was observed and based on its dependence on frequency and duty cycle, ascribed to trapping and de-trapping processes at the interface of the emissive layer and electron blocker. The result suggests that the exciton recombination zone is at, or close to the interface between the emissive layer and electron blocker. The lifetime of the thin films of phosphorescent emitter Pt(ptp)2 were studied for comparison with rare earth emitter Eu(hfa)3. The lifetime of 65% Pt(ptp)2:CBP co-film was around 638 nanoseconds at the emission peak of 572nm, and the lifetime of neat Eu(hfa)3 film was obtained around 1 millisecond at 616 nm, which supports the enhanced efficiency obtained from the Pt(ptp)2 devices. The long lifetime and narrow emission of the rare earth dopant Eu(hfa)3 is a fundamental factor limiting device performance. Red …

Low-dielectric (k) films are one of the performance drivers for continued scaling of integrated circuit devices. These films are needed in microelectronic device interconnects to lower power consumption and minimize cross talk between metal lines that "interconnect" transistors. Low-k materials currently in production for the 45 and 65 nm node are most often organosilicate glasses (OSG) with dielectric constants near 2.8 and nominal porosities of 8-10%. The next generation of low-k materials will require k values 2.6 and below for the 45 nm device generation and beyond. The continuous decrease in device dimensions in ultra large scale integrated (ULSI) circuits have brought about the replacement of the silicon dioxide interconnect dielectric (ILD), which has a dielectric constant (k) of approximately 4.1, with low dielectric constant materials. Lowering the dielectric constant reduces the propagation delays, RC constant (R = the resistance of the metal lines; C = the line capacitance), and metal cross-talk between wires. In order to reduce the RC constants, a number of low-k materials have been studied for use as intermetal dielectrics. The k values of these dielectric materials can be lowered by replacing oxide films with carbon-based polymer films, incorporating hydrocarbon functional groups into oxide films (SiOCH …

Friction and wear mitigation is typically accomplished by introducing a shear accommodating layer (e.g., a thin film of liquid) between surfaces in sliding and/or rolling contacts. When the operating conditions are beyond the liquid realm, attention turns to solid coatings. Solid lubricants have been widely used in governmental and industrial applications for mitigation of wear and friction (tribological properties). Conventional examples of solid lubricants are MoS2, WS2, h-BN, and graphite; however, these and some others mostly perform best only for a limited range of operating conditions, e.g. ambient air versus dry nitrogen and room temperature versus high temperatures. Conversely, lubricious oxides have been studied lately as good potential candidates for solid lubricants because they are thermodynamically stable and environmentally robust. Oxide surfaces are generally inert and typically do not form strong adhesive bonds like metals/alloys in tribological contacts. Typical of these oxides is ZnO. The interest in ZnO is due to its potential for utility in a variety of applications. To this end, nanolaminates of ZnO, Al2O3, ZrO2 thin films have been deposited at varying sequences and thicknesses on silicon substrates and high temperature (M50) bearing steels by atomic layer deposition (ALD). The top lubricious, nanocrystalline ZnO layer was structurally-engineered …

Carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) are attractive reinforcements for lightweight and high strength metal matrix composites due to their excellent mechanical and physical properties. The present work is an attempt towards investigating the effect of CNT and GNP reinforcements on the mechanical properties of nickel matrix composites. The CNT/Ni (dry milled) nanocomposites exhibiting a tensile yield strength of 350 MPa (about two times that of SPS processed monolithic nickel ~ 160 MPa) and an elongation to failure ~ 30%. In contrast, CNT/Ni (molecular level mixed) exhibited substantially higher tensile yield strength (~ 690 MPa) but limited ductility with an elongation to failure ~ 8%. The Ni-1vol%GNP (dry milled) nanocomposite exhibited the best balance of properties in terms of strength and ductility. The enhancement in the tensile strength (i.e. 370 MPa) and substantial ductility (~40%) of Ni-1vol%GNP nanocomposites was achieved due to the combined effects of grain refinement, homogeneous dispersion of GNPs in the nickel matrix, and well-bonded Ni-GNP interface, which effectively transfers stress across metal-GNP interface during tensile deformation. A second emphasis of this work was on the detailed 3D microstructural characterization of a new class of Ni-Ti-C based metal matrix composites, developed using the laser engineered net …

We are facing an energy crisis because of the limitation of the fossil fuel and the pollution caused by burning it. Clean energy technologies, such as fuel cells and metal-air batteries, are studied extensively because of this high efficiency and less pollution. Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential in the process of energy storage and conversion, and noble metals (e.g. Pt) are needed to catalyze the critical chemical reactions in these devices. Functionalized carbon nanomaterials such as heteroatom-doped and molecule-adsorbed graphene can be used as metal-free catalysts to replace the expensive and scarce platinum-based catalysts for the energy storage and conversion. Traditionally, experimental studies on the catalytic performance of carbon nanomaterials have been conducted extensively, however, there is a lack of computational studies to guide the experiments for rapid search for the best catalysts. In addition, theoretical mechanism and the rational design principle towards ORR and OER also need to be fully understood. In this dissertation, density functional theory calculations are performed to calculate the thermodynamic and electrochemical properties of heteroatom-doped graphene and molecule-adsorbed graphene for ORR and OER. Gibb's free energy, overpotential, charge transfer and edge effect are evaluated. The charge transfer analysis show …

The penchant towards development of high performance materials for light weighting engineering systems through various thermomechanical processing routes has been soaring vigorously. Friction stir processing (FSP) - a relatively new thermomechanical processing route had shown an excellent promise towards microstructural modification in many Al and Mg alloy systems. Nevertheless, the expansion of this process to high temperature materials like titanium alloys and steels is restricted by the limited availability of tool materials. Despite it challenges, the current thesis sets a tone for the usage of FSP to tailor the mechanical properties in titanium alloys and steels. FSP was carried out on three near beta titanium alloys, namely Ti6246, Ti185 and Tiβc with increasing β stability index, using various tool rotation rates and at a constant tool traverse speed. Microstructure and mechanical property relationship was studied using experimental techniques such as SEM, TEM, mini tensile testing and synchrotron x-ray diffraction. Two step aging on Ti6246 had resulted in an UTS of 2.2GPa and a specific strength around 500 MPa m3/mg, which is about 40% greater than any commercially available metallic material. Similarly, FSP on an ultra-high strength steel―Eglin steel had resulted in a strength greater than 2GPa with a ductility close …

The high temperature BCC phase (b) of titanium undergoes a martensitic transformation to HCP phase (a) upon cooling, but can be stabilized at room temperature by alloying with BCC transition metals such as Mo. There exists a metastable composition range within which the alloyed b phase separates into a + b upon equilibrium cooling but not when rapidly quenched. Compositional partitioning of the stabilizing element in as-quenched b microstructure creates nanoscale precipitates of a new simple hexagonal w phase, which considerably reduces ductility. These phase transformation reactions have been extensively studied experimentally, yet several significant questions remain: (i) The mechanism by which the alloying element stabilizes the b phase, thwarts its transformation to w, and how these processes vary as a function of the concentration of the stabilizing element is unclear. (ii) What is the atomistic mechanism responsible for the non-Arrhenius, anomalous diffusion widely observed in experiments, and how does it extend to low temperatures? How does the concentration of the stabilizing elements alter this behavior? There are many other w forming alloys that such exhibit anomalous diffusion behavior. (iii) A lack of clarity remains on whether w can transform to a -phase in the crystal bulk or if it …

Hard gold thin films and coatings are widely used in electronics as an effective material to reduce the friction and wear of relatively less expensive electrically conductive materials while simultaneously seeking to provide oxidation resistance and stable sliding electrical contact resistance (ECR). The main focus of this dissertation was to synthesize nanocrystalline Au films with grain structures capable of remaining stable during thermal exposure and under sliding electrical contact stress and the passing of electrical current. Here we have utilized a physical vapor deposition (PVD) technique, electron beam evaporation, to synthesize Au films modified by ion implantation and codeposited ZnO hardened Au nanocomposites. Simultaneous friction and ECR experiments of low fluence (< 1x10^17 cm^-2) He and Ar ion implanted Au films showed reduction in friction coefficients from ~1.5 to ~0.5 and specific wear rates from ~4x10^-3 to ~6x10^-5 mm^3/N·m versus as-deposited Au films without significant change in sliding ECR (~16 mΩ). Subsurface microstructural changes of He implanted films due to tribological stress were analyzed via site-specific cross-sectional transmission electron microscopy (TEM) and revealed the formation of nanocrystalline grains for low energy (22.5 keV) implantation conditions as well as the growth and redistribution of cavities. Nanoindentation hardness results revealed an increase …

Due to the wide application of silica based systems ranging from microelectronics to nuclear waste disposal, detailed knowledge of water-silica interactions plays an important role in understanding fundamental processes, such as glass corrosion and the long term reliability of devices. In this dissertation, atomistic computer simulation methods have been used to explore and identify the mechanisms of water-silica reactions and the detailed processes that control the properties of the water-silica interfaces due to their ability to provide atomic level details of the structure and reaction pathways. The main challenges of the amorphous nature of the silica based systems and nano-porosity of the structures were overcome by a combination of simulation methodologies based on classical molecular dynamics (MD) simulations with Reactive Force Field (ReaxFF) and density functional theory (DFT) based ab initio MD simulations. Through the development of nanoporous amorphous silica structure models, the interactions between water and the complex unhydroxylated internal surfaces identified the unusual stability of strained siloxane bonds in high energy ring structure defects, as well as the hydroxylation reaction kinetics, which suggests the difficulty in using DFT methods to simulate Si-O bond breakage with reasonable efficiency. Another important problem addressed is the development of silica gel structures …

The recent emphasis on magnesium alloys can be appreciated by following the research push from several agencies, universities and editorial efforts. With a density equal to two-thirds of Al and one-thirds of steel, Mg provides the best opportunity for lightweighting of metallic components. However, one key bottleneck restricting its insertion into industrial applications is low strength values. In this respect, Mg-Y-Nd alloys have been promising due to their ability to form strengthening precipitates on the prismatic plane. However, if the strength is compared to Al alloys, these alloys are not attractive. The primary reason for low structural performance in Mg is related to low alloying and microstructural efficiency. In this dissertation, these terminologies are discussed in detail. A simple calculation showed that the microstructural efficiency in Mg-4Y-3Nd alloy is 30% of its maximum potential. Guided by the definitions of alloying and microstructural efficiency, the two prime objectives of this thesis were to: (i) to use thermomechanical processing routes to tailor the microstructure and achieve high strength in an Mg-4Y-3Nd alloy, and (ii) optimize the alloy chemistry of the Mg-rare earth alloy and design a novel rare—earth free Mg alloy by Calphad approach to achieve a strength of 500 MPa. Experimental, …

Since NiTi shape memory alloy (SMA) was discovered in the early 1960s, great progress has been made in understanding the properties and mechanisms of NiTi SMA and in developing associated products. For several decades, most of the scientific research and industrial interests on NiTi SMA has focused on its superelastic applications in the biomedical field and shape memory based “smart” devices, which involves the low strain rate (around 0.001 s^-1) response of NiTi SMA. Due to either stress-induced martensite phase transformation or stress induced martensite variant reorientation under the applied load, NiTi SMA has exhibited a high damping capacity in both austenitic and martensitic phase. Recently, there has been an increasing interest in exploitation of the high damping capacity of NiTi SMA to develop high strain rate related applications such as seismic damping elements and energy absorbing devices. However, a systematic study on the influence of strain, strain rate and temperature on the mechanical properties, phase transformation, microstructure and crystal structure is still limited, which leads to the difficulties in the design of products being subjected to high strain rate loading conditions. The four main objectives of the current research are: (1) achieve the single loading and the control of …

Metal fatigue is a recurring problem for metallurgists and materials engineers, especially in structural applications. It has been responsible for many disastrous accidents and tragedies in history. Understanding the micro-mechanisms during cyclic deformation and combating fatigue failure has remained a grand challenge. Environmental effects, like temperature or a corrosive medium, further worsen and complicate the problem. Ultimate design against fatigue must come from a materials perspective with a fundamental understanding of the interaction of microstructural features with dislocations, under the influence of stress, temperature, and other factors. This research endeavors to contribute to the current understanding of the fatigue failure mechanisms. Cast aluminum alloys are susceptible to fatigue failure due to the presence of defects in the microstructure like casting porosities, non-metallic inclusions, non-uniform distribution of secondary phases, etc. Friction stir processing (FSP), an emerging solid state processing technique, is an effective tool to refine and homogenize the cast microstructure of an alloy. In this work, the effect of FSP on the microstructure of an A356 cast aluminum alloy, and the resulting effect on its tensile and fatigue behavior have been studied. The main focus is on crack initiation and propagation mechanisms, and how stage I and stage II cracks …

Magnesium and its alloys have been considered for load-bearing implant materials due to their similar mechanical properties to the natural bone, excellent biocompatibility, good bioactivity, and biodegradation. Nevertheless, the uncontrollable corrosion rate in biological environment restrains their application. Hydroxyapatite (HA, Ca10(PO4)6(OH)2) is a widely used bio-ceramic which has bone-like mineral structure for bone fixation. Poor fracture toughness of HA makes it not suitable for load-bearing application as a bulk. Thus, HA is introduced into metallic surface in various forms for improving biocompatibility. Recently friction stir processing (FSP) has emerged as a surface modification tool for surface/substrate grain refinement and homogenization of microstructure in biomaterial. In the pressent efforts, Mg-nHA composite surface on with 5-20 wt% HA on Mg substrate were fabricated by FSP for biodegradation and bioactivity study. The results of electrochemical measurement indicated that lower amount (~5% wt%) of Ca in Mg matrix can enhance surface localized corrosion resistance. The effects of microstructure,the presence of HA particle and Mg-Ca intermetallic phase precipitates on in vitro behavior of Mg alloy were investigated by TEM, SEM, EDX,XRD ,and XPS. The detailed observations will be discussed during presentation.

Geckos are famous for the skill of switchable adhesion that they use to stick on various surface while keep their fingers super clean. In the dissertation, a unique mechanism was discovered to explain gecko self-cleaning phenomena. Using atomic force microscopy (AFM), we managed to compare the microparticle-substrate adhesion and the microparticle-seta adhesion with a single seta bonded to the AFM cantilever. A dynamic effect was approved that high pulling-off speed could increase the microparticle-substrate adhesion and thus the self-cleaning appears at high moving speed. Based on the self-cleaning theory, a gecko-inspired N-doped graphene surface with switchable adhesion was achieved, which was designed into a bio-inspired micromanipulator with a success rate over 90%. When electrical bias was applied on this biomimetic surface, the charge concentration induced an electrical double layer (ELD) on the convex surfaces, which attracts polar water molecules to form a water bridge on it, significantly enhancing the adhesion on the wrinkled graphene surface, mimicking the capillary force on beetle feet. Therefore, the bio-inspired adhesive surface can be controlled with speed, electrical bias, humidity and different material surfaces. The water attraction phenomenon on the polarized surface was further tested for the potential application of water collection and evaporation in …

High entropy alloys (HEAs) is a concept wherein alloys are constructed with five or more elements mixed in equal proportions; these are also known as multi-principle elements (MPEs) or complex concentrated alloys (CCAs). This PhD thesis dissertation presents research conducted to develop precipitation-hardenable high entropy alloys using a much-studied fcc-based equi-atomic quaternary alloy (CoCrFeNi). Minor additions of aluminium make the alloy amenable for precipitating ordered intermetallic phases in an fcc matrix. Aluminum also affects grain growth kinetics and Hall-Petch hardenability. The use of a combinatorial approach for assessing composition-microstructure-property relationships in high entropy alloys, or more broadly in complex concentrated alloys; using laser deposited compositionally graded AlxCrCuFeNi2 (0 < x < 1.5) complex concentrated alloys as a candidate system. The composition gradient has been achieved from CrCuFeNi2 to Al1.5CrCuFeNi2 over a length of ~25 mm, deposited using the laser engineered net shaping process from a blend of elemental powders. With increasing Al content, there was a gradual change from an fcc-based microstructure (including the ordered L12 phase) to a bcc-based microstructure (including the ordered B2 phase), accompanied with a progressive increase in microhardness. Based on this combinatorial assessment, two promising fcc-based precipitation strengthened systems have been identified; Al0.3CuCrFeNi2 and Al0.3CoCrFeNi, …

NiTi-based shape memory alloys (SMAs) offer a good combination of high-strength, ductility, corrosion resistance, and biocompatibility that has served them well and attracted the attention of many researchers and industries. The alloys unique thermo-mechanical ability to recover their initial shape after relatively large deformations by heating or upon unloading due to a characteristic reversible phase transformation makes them useful as damping devices, solid state actuators, couplings, etc. However, there is a need to increase the temperature of the characteristic phase transformation above 150 °C, especially in the aerospace industry where high temperatures are often seen. Prior researchers have shown that adding ternary elements (Pt, Pd, Au, Hf and Zr) to NiTi can increase transformation temperatures but most of these additions are extremely expensive, creating a need to produce cost-effective high temperature shape memory alloys (HTSMAs). Thus, the main objective of this research is to examine the relatively unstudied NiTiZr system for the ability to produce a cost effective and formable HTSMA. Transformation temperatures, precipitation paths, processability, and high-temperature oxidation are examined, specifically using high energy X-ray Diffraction (XRD) measurements, in NiTi-20 at.% Zr. This is followed by an in situ XRD study of the phase growth kinetics of the favorable …

Magnesium and its alloys are considered as the potential biomaterials due to their biocompatibility and biodegradable characteristics but suffer from poor corrosion performance. Various surface modification techniques are employed to improve their corrosion resistance. In present case, laser surface melting was carried out on AZ31B Mg alloy with various laser energy densities using a continuous wave ytterbium laser. Effect of laser treatment on phase and microstructure evolution was evaluated by X ray diffraction and scanning electron microscopy. Multi-physics thermal model predicted time temperature evolution along the depth of the laser treatment zone. Additionally, electrochemical method and bio-immersion test were employed to evaluate the corrosion behavior in simulated body fluid medium. Microstructure revealed grain refinement and even distribution of Mg17Al12 phase along the grain boundary for laser treated samples leading to substantial enhancement in the corrosion resistance of the laser treated samples compared to the untreated alloy. The laser processed samples also possessed a superior wettability in SBF solution than the untreated sample. This was further reflected in enhanced bio-integration behavior of laser processed samples. By changing the parameters of laser processing such as power, scanning speed, and fill spacing, a controllable corrosion resistance and bioactivity/biocompatibility of the implant material was …

The principal objective of this work was to elucidate the effect of microstructural features on the intrinsic dislocation mechanisms in two FCC alloys. First alloy Al0.1CoCrFeNi was from a new class of material known as complex concentrated alloys, particularly high entropy alloys (HEA). The second was a conventional Al-Mg-Sc alloy in ultrafine-grained (UFG) condition. In the case of HEA, the lattice possess significant lattice strain due to the atomic size variation and cohesive energy differences. Moreover, both the lattice friction stress and the Peierls barrier height are significantly larger than the conventional FCC metals and alloys. The experimental evidences, so far, provide a distinctive identity to the nature and motion of dislocations in FCC HEA as compared to the conventional FCC metals and alloys. Hence, the thermally activated dislocation mechanisms and kinetics in HEA has been studied in detail. To achieve the aim of examining the dislocation kinetics, transient tests, both strain rate jump tests and stress relaxation tests, were conducted. Anomalous behavior in dislocation kinetics was observed. Surprisingly, a large rate sensitivity of the flow stress and low activation volume of dislocations were observed, which are unparalleled as compared to conventional CG FCC metals and alloys. The observed trend …

In this dissertation, density functional theory calculations are performed to calculate the thermodynamic and electrochemical properties of metal coordinated frameworks for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Gibb's free energy, overpotential, charge transfer and ligands effect are evaluated. The charge transfer analysis shows the positive charges on the metal coordinated frameworks play an essential role in improving the electrochemical properties of the metal coordinated frameworks. Based on the calculations, design principles are introduced to rationally design and predict the electrochemical properties of metal coordinated frameworks as efficient catalysts for ORR and OER. An intrinsic descriptor is discovered for the first time, which can be used as a materials parameter for rational design of the metal coordinated frameworks for energy storage and conversion. The success of the design principles provides a better understanding of the mechanism behind ORR and OER and a screening approach for the best catalyst for energy storage and conversion.

Geckos can freely climb on walls and ceilings against their body weight at speed of over 1ms-1. Switching between attachment and detachment seem simple and easy for geckos, without considering the surface to be dry or wet, smooth or rough, dirty or clean. In addition, gecko can shed dirt particles during use, keeping the adhesive pads clean. Mimicking this biological system can lead to a new class of dry adhesives for various applications. However, gecko’s unique dry self-cleaning mechanism remains unknown, which impedes the development of self-cleaning dry adhesives. In this dissertation we provide new evidence and self-cleaning mechanism to explain how gecko shed particles and keep its sticky feet clean. First we studied the dynamic enhancement observed between micro-sized particles and substrate under dry and wet conditions. The adhesion force of soft (polystyrene) and hard (SiO2 and Al2O3) micro-particles on soft (polystyrene) and hard (fused silica and sapphire) substrates was measured using an atomic force microscope (AFM) with retraction (z-piezo) speed ranging over 4 orders of magnitude. The adhesion is strongly enhanced by the dynamic effect. When the retraction speeds varies from 0.02 µm/s to 156 µm/s, the adhesion force increases by 10% ~ 50% in dry nitrogen while …

The high energy lasers are emerging as an innovative material processing tool to effectively fabricate complex shapes on the hard and brittle structural ceramics, which previously had been near impossible to be machined effectively using various conventional machining techniques. In addition, the in-situ measurement of the thermo-physical properties in the severe laser machining conditions (high temperature, short time duration, and small interaction volume) is an extremely difficult task. As a consequence, it is extremely challenging to investigate the evolution of surface topography through experimental analyses. To address this issue, an integrated experimental and computational (multistep and multiphysics based finite-element modeling) approach was employed to understand the influence of laser processing parameters to effectively control the various thermo-physical effects (recoil pressure, Marangoni convection, and surface tension) during transient physical processes (melting, vaporization) for controlled surface topography (surface finish). The results indicated that the material lost due to evaporation causes an increase in crater depth of machined cavity, whereas liquid expulsion created by the recoil pressure increases the material pileup height around the lip of machined cavity, the major attributes of surface topography (roughness). Also, it was found that the surface roughness increased with increase in laser energy density and pulse rate …