A Comparison Between Graphene and WS2 as Solid Lubricant Additives to Aluminum for Automobile Applications

The purpose of this thesis was to compare graphene nanoplatelets (GNP) and WS2 as solid lubricant additives to aluminum in order to reduce friction and wear. The central hypothesis of this work relied on lubricating properties of 2D materials, which consist layers that slip under a shear force. Two aluminum composites were made (Al-2 vol.% GNP and Al-2 vol.% WS2) by spark plasma sintering. Tribological properties were evaluated by ball-on-disk wear tests at room temperature (RT) and 200°C. WS2 not only presented the lowest COF (0.66) but also improved the wear resistance of aluminum by 54% at RT. Al-2 vol.% GNP composite displayed poor densification (91%) and low hardness resulting in poor wear resistance. The wear rate of Al-2 vol.% GNP composite increased by 233% at RT and 48% at 200°C as compared to pure aluminum. GNP addition also resulted in lower COF (0.79) as compared to pure aluminum (0.87).

In-Vivo Corrosion and Fretting of Modular TI-6AL-4V/CO-CR-MO Hip Prostheses: The Influence of Microstructure and Design Parameters

The purpose of this study was to evaluate the incidence of corrosion and fretting in 48 retrieved titanium-6aluminum-4vanadium and/or cobalt-chromium-molybdenum modular total hip prosthesis with respect to alloy material microstructure and design parameters. The results revealed vastly different performance results for the wide array of microstructures examined. Severe corrosion/fretting was seen in 100% of as-cast, 24% of low carbon wrought, 9% of high carbon wrought and 5% of solution heat treated cobalt-chrome. Severe corrosion/fretting was observed in 60% of Ti-6Al-4V components. Design features which allow for fluid entry and stagnation, amplification of contact pressure and/or increased micromotion were also shown to play a role. 75% of prosthesis with high femoral head-trunnion offset exhibited poor performance compared to 15% with a low offset. Large femoral heads (>32mm) did not exhibit poor corrosion or fretting. Implantation time was not sufficient to cause poor performance; 54% of prosthesis with greater than 10 years in-vivo demonstrated none or mild corrosion/fretting.

Study of Ammonia Borane and its Derivatives: Influence of Nanoconfinements and Pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ~140 degree Celcius and ~0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ~125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ~13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.

Synthesis of copper carbon nanotube composite and its electrical conductivity measurement

The matrices in which Multi Walled Carbon Nanotubes (MWCNTs) are incorporated to produce composites with improved electrical properties can be polymer, metal or metal oxide. Most composites containing CNTs are polymer based because of its flexibility in fabrication. Very few investigations have been focused on CNT-metal composites due to fabrication difficulties, such as achievement of homogeneous distribution of MWCNTs and poor interfacial bonding between MWCNTs and the metal matrix. In an effort to overcome poor interfacial bonding for the Cu - MWCNT composite, silver (Ag) and nickel (Ni) resinates have been incorporated in the ball milling stage. Composites of MWCNT (16, 12, and 8 Vol %) - Cu+Ag+Ni were pelleted at 20,000 psi (669.4 Mpa) and sintered at 950 °C. The electrical conductivity results measured by four probe meter showed that the conductivity decreases with increase in the porosity. Moreover from these results it can also be stated that an addition of optimum value of (12 Vol %) MWCNT leads to high electrical conductivity (9.26E+07 s-m"), which is 50% greater than the conductivity of Cu. It is anticipated that the conductivity can be increased substantially with hot isostatic pressing of the pellet.

Oxidation and tensile behavior of ferritic/martensitic steels after exposure to lead-bismuth eutectic

Two ferritic/martensitic steels, T91 steel and newly developed SIMP steel, were subject to tensile test after being oxidized in the liquid lead-bismuth eutectic (LBE) at 873 K for 500 h, 1000 h and 2000 h. Tensile tests were also carried out on the steels only thermally aged at 873 K. The result shows that thermal aging has no effect. Exposure to LBE at 873 K leads to a slight decrease in strength, but a large decrease in elongation when tested at 873 K. When tested at 873 K after 2000 h exposure, the tensile strength of T91 decreases slightly, and elongation from 39% to 21%. For SIMP, the decreases are slightly and from 44% to 28%, for tensile strength and elongation, respectively. The room temperature strength has slightly larger percentage reductions after the LBE exposure, but the elongation changes little.

Green Composites and Their Properties: A Brief Introduction

Green composites are important class of biocomposites widely explored due to their enhanced properties. The biodegradable polymeric material is reinforced with natural fibers to form a composite that is eco-friendly and environment sustainable. The green composites have potential to attract the traditional petroleum-based composites which are toxic and nonbiodegradable. The green composites eliminate the traditional materials such as steel and wood with biodegradable polymer composites. The degradable and environment-friendly green composites were prepared by various fabrication techniques. The various properties of different fiber composite were studied as reinforcement for fully biodegradable and environmental-friendly green composites.

Techno-Economic and Life Cycle Assessment for the Production of Green Composites

Botanically, green composites belong to an economically important seed plant family that includes maize, wheat, rice, and sorghum known as Saccharum offi cinarum. There are so many natural fibers available in the environment such as rice husk, hemp fibers, flax fibers, bamboo fibers, coconut fiber, coconut coir, grawia optiva and many others also. Life Cycle Assessment (LCA) is a process to estimate the environmental feature and potential impacts related to a product, by organizing a directory of pertinent inputs and outputs of a product system, assessing the potential environmental impacts related with the said inputs and outputs, explaining the results of the inventory analysis and impact evaluation phases in connection to the objectives of the study. Particularly Bagasse, an agricultural residue not only becomes a problem from the environmental point of view, but also affects the profitability of the sugarcane industries. This chapter discusses the properties, processing methods and various other aspects including economic and environmental aspects related to green composites.

Synthesis and evaluation of temperature- and glucose-sensitive nanoparticles based on phenylboronic acid and N-vinylcaprolactam for insulin delivery

Poly N-vinylcaprolactam-co-acrylamidophenylboronic acid p(NVCL-co-AAPBA) was prepared from N-vinylcaprolactam (NVCL) and 3-acrylamidophenylboronic acid (AAPBA), using 2,2-azobisisobutyronitrile (AIBN) as initiator. The synthesis and structure of the polymer were examined by Fourier Transform infrared spectroscopy (FT-IR) and 1H-NMR. Dynamic light scattering (DLS), lower critical solution temperature (LCST) and transmission electron microscopy (TEM) were utilized to characterize the nanoparticles, CD spectroscopy was used to determine if there were any changes to the conformation of the insulin, and cell and animal toxicity were also investigated. The prepared nanoparticles were found to be monodisperse submicron particles and were glucose- and temperature-sensitive. In addition, the nanoparticles have good insulin-loading characteristics, do not affect the conformation of the insulin and show low-toxicity to cells and animals. These p(NVCL-co-AAPBA) nanoparticles may have some value for insulin or other hypoglycemic protein delivery.

X-Ray Absorption Spectroscopy and Computer Modelling Study of Nanocrystalline Binary Alkaline Earth Fluorides

Nanocrystalline samples of Ba1-xCaxF2 prepared by high-energy milling show an unusually high F-ion conductivity, which exhibit a maximum in the magnitude and a minimum in the activation energy at x = 0.5. Here, we report an X-ray absorption spectroscopy (XAS) at the Ca and Sr K edges and the Ba L-3 edge and a molecular dynamics (MD) simulation study of the pure and mixed fluorides. The XAS measurements on the pure binary fluorides, CaF2, SrF2 and BaF2 show that high-energy ball-milling produces very little amorphous material, in contrast to the results for ball milled oxides. XAS measurements of Ba1-xCaxF2 reveal that for 0 < x < 1 there is considerable disorder in the local environments of the cations which is highest for x = 0.5. Hence the maximum in the conductivity corresponds to the composition with the maximum level of local disorder. The MD calculations also show a highly disordered structure consistent with the XAS results and similarly showing maximum disorder at x = 0.5.

Effect of rare earth dopants on structural and mechanical properties of nanoceria synthesized by combustion method

Structural characteristics of combustion synthesized, calcined and densified pure and doped nanoceria with tri-valent cations of Er, Y, Gd, Sm and Nd were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The results showed that the as-synthesized and calcined nanopowders were mesoporous and calculated lattice parameters were close to theoretical ion-packing model. The effect of dopants on elastic modulus, microhardness and fracture toughness of sintered pure and doped ceria were investigated. It was observed that tri-valent cation dopants increased the hardness of the ceria, whereas the fracture toughness and elastic modulus were decreased.

IN-SITU ELECTRICAL, MECHANICAL AND ELECTROCHEMICAL CHARACTERIZATIONS OF ONE-DIMENSIONAL NANOSTRUCTURES

One-dimensional nanostructures initiated new aspects to the materials applications due to their superior properties compared to the bulk materials. Properties of nanostructures have been characterized by many techniques and used for various device applications. However, simultaneous correlation between the physical and structural properties of these nanomaterials has not been widely investigated. Therefore, it is necessary to perform in-situ study on the physical and structural properties of nanomaterials to understand their relation. In this work, we will use a unique instrument to perform real time atomic force microscopy (AFM) and scanning tunneling microscopy (STM) of nanomaterials inside a transmission electron microscopy (TEM) system. This AFM/STM-TEM system is used to investigate the mechanical, electrical, and electrochemical properties of boron nitride nanotubes (BNNTs) and Silicon nanorods (SiNRs). BNNTs are one of the subjects of this PhD research due to their comparable, and in some cases superior, properties compared to carbon nanotubes. Therefore, to further develop their applications, it is required to investigate these characteristics in atomic level. In this research, the mechanical properties of multi-walled BNNTs were first studied. Several tests were designed to study and characterize their real-time deformation behavior to the applied force. Observations revealed that BNNTs possess highly flexible structures under applied force. Detailed studies were then conducted to understand the bending mechanism of the BNNTs. Formations of reversible ripples were observed and described in terms of thermodynamic energy of the system. Fracture failure of BNNTs were initiated at the outermost walls and characterized to be brittle. Second, the electrical properties of individual BNNTs were studied. Results showed that the bandgap and electronic properties of BNNTs can be engineered by means of applied strain. It was found that the conductivity, electron concentration and carrier mobility of BNNTs can be tuned as a function of applied stress. Although, BNNTs are considered to be candidate for field emission applications, observations revealed that their properties degrade upon cycles of emissions. Results showed that due to the high emission current density, the temperature of the sample was increased and reached to the decomposition temperature at which the B-N bonds start to break. In addition to BNNTs, we have also performed in-situ study on the electrochemical properties of silicon nanorods (SiNRs). Specifically, lithiation and delithiation of SiNRs were studied by our STM-TEM system. Our observations showed the direct formation of Li22Si5 phases as a result of lithium intercalation. Radial expansion of the anode materials were observed and characterized in terms of size-scale. Later, the formation and growth of the lithium fibers on the surface of the anode materials were observed and studied. Results revealed the formation of lithium islands inside the ionic liquid electrolyte which then grew as Li dendrite toward the cathode material.

DEVELOPMENT OF PRECIPITATION HARDENABLE AL-SC-ZR-HF QUATERNARY ALLOYS THROUGH THERMODYNAMIC MODELING, AND ROOM-TEMPERATURE AND ELEVATED TEMPERATURE HARDNESS

Aluminum alloyed with small atomic fractions of Sc, Zr, and Hf has been shown to exhibit high temperature microstructural stability that may improve high temperature mechanical behavior. These quaternary alloys were designed using thermodynamic modeling to increase the volume fraction of precipitated tri-aluminide phases to improve thermal stability. When aged during a multi-step, isochronal heat treatment, two compositions showed a secondary room-temperature hardness peak up to 700 MPa at 450°C. Elevated temperature hardness profiles also indicated an increase in hardness from 200-300°C, attributed to the precipitation of Al3Sc, however, no secondary hardness response was observed from the Al3Zr or Al3Hf phases in this alloy.

DESIGN, SYNTHESIS AND APPLICATIONS OF FLUORESCENT AND ELECTROCHEMICAL PROBES

“Seeing is believing” the proverb well suits for fluorescent imaging probes. Since we can selectively and sensitively visualize small biomolecules, organelles such as lysosomes, neutral molecules, metal ions, anions through cellular imaging, fluorescent probes can help shed light on the physiological and pathophysiological path ways. Since these biomolecules are produced in low concentrations in the biochemical pathways, general analytical techniques either fail to detect or are not sensitive enough to differentiate the relative concentrations. During my Ph.D. study, I exploited synthetic organic techniques to design and synthesize fluorescent probes with desirable properties such as high water solubility, high sensitivity and with varying fluorescent quantum yields. I synthesized a highly water soluble BOIDPY-based turn-on fluorescent probe for endogenous nitric oxide. I also synthesized a series of cell membrane permeable near infrared (NIR) pH activatable fluorescent probes for lysosomal pH sensing. Fluorescent dyes are molecular tools for designing fluorescent bio imaging probes. This prompted me to design and synthesize a hybrid fluorescent dye with a functionalizable chlorine atom and tested the chlorine re-activity for fluorescent probe design. Carbohydrate and protein interactions are key for many biological processes, such as viral and bacterial infections, cell recognition and adhesion, and immune response. Among several analytical techniques aimed to study these interactions, electrochemical bio sensing is more efficient due to its low cost, ease of operation, and possibility for miniaturization. During my Ph.D., I synthesized mannose bearing aniline molecule which is successfully tested as electrochemical bio sensor. A Ferrocene-mannose conjugate with an anchoring group is synthesized, which can be used as a potential electrochemical biosensor.

Intergranular Corrosion and Stress Corrosion Cracking of Extruded AA6005A

A research program focused on understanding the intergranular corrosion (IGC) and stress corrosion cracking (SCC) behavior of AA6005A aluminum extrusions is presented in this dissertation. The relationship between IGC and SCC susceptibility and the mechanisms of SCC in AA6005A extrusions were studied by examining two primary hypotheses. IGC susceptibility of the elongated grain structure in AA6005A exposed to low pH saltwater was found to depend primarily on the morphology of Cu-containing precipitates adjacent to the grain boundaries in the elongated grain structure. IGC susceptibility was observed when a continuous (or semi-continuous) film of Cu-containing phase was present along the grain boundaries. When this film coarsened to form discrete Cu-rich precipitates, no IGC was observed. The morphology of the Cu-rich phase depended on post-extrusion heat treatment. The rate of IGC penetration in the elongated grain structure of AA6005A-T4 and AA6005A-T6 extrusions was found to be anisotropic with IGC propagating most rapidly along the extrusion direction, and least rapidly along the through thickness direction. A simple 3-dimensional geometric model of the elongated grain structure was accurately described the observed IGC anisotropy, therefore it was concluded that the anisotropic IGC susceptibility in the elongated grain structure was primarily due to geometric elongation of the grains. The velocity of IGC penetration along all directions in AA6005A-T6 decreased with exposure time. Characterization of the local environment within simulated corrosion paths revealed that a pH gradient existed between the tip of the IGC path and the external environment. Knowledge of the local environment within an IGC path allowed development of a simple model based on Fick's first law that considered diffusion of Al3+ away from the tip of the IGC path. The predicted IGC velocity agreed well with the observed IGC velocity, therefore it was determined that diffusion of Al3+ was the primary factor in determining the velocity of IGC penetration. The velocity of crack growth in compact tensile (CT) specimens of AA6005A-T6 extrusion exposed to 3.5% NaCl at pH = 1.5 was nearly constant over a range of applied stress intensities, exposure times, and crack lengths. The crack growth behavior of CT specimens of AA6005A-T6 extrusion exposed to a solution of 3.5% NaCl at pH = 2.0 exhibited similar behavior, but the crack velocity was ~10.5X smaller than that those exposed to a solution at pH =1.5. Analysis of the local stress state and polarization behavior at the crack tip predicted that increasing the pH of the bulk solution from 1.5 to 2.0 would decrease the corrosion current density at the crack tip by approximately 11.8X. This predicted decrease in corrosion current density was in reasonable agreement with the observed decrease in SCC velocity associated with increasing the solution pH from 1.5 to 2.0. The agreement between the predicted and observed SCC velocities suggested that the electrochemical reactions controlling SCC in AA6005A-T6 extrusions are ultimately controlled by the pH gradient that exists between the crack tip and external environment.