The main goal of this thesis is to deposit metal particles on the surface of 2D nanoplatelets using a controlled cementation process. As a proof of concept, copper (Cu) and Graphene Nanoplatelets (GNP) were chosen as the representative metal and 2D nanoplatelets, respectively. Specific goals of this study include depositing nanometer scale Cu particles on the surface of GNP at a low concentration (approximately 5 vol.%) while maintaining clustering and impurities at a minimum. Parametric studies were done to attain these goals by investigating various metallic reducer types and morphologies, GNP surface activation process, acid volume % and copper (II) sulfate concentrations. Optimal conditions were obtained with Mg ribbon as a reducer, 3 minutes of activation, 1 vol.% of acetic acid and 0.01 M CuSO4. The GNP-Cu powder synthesized in this work is a precursor material to be consolidated via spark plasma sintering (SPS) to make a nacre-like, layered structure for future studies.

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.

Fossil fuels constitute a significant fraction of the world’s energy demand. The burning of fossil fuels emits huge amounts of carbon dioxide into the atmosphere. Therefore, the limited availability of fossil fuel resources and the environmental impact of their use require a change to alternative energy sources or carriers (such as hydrogen) in the foreseeable future. The development of methods to mitigate carbon dioxide emission into the atmosphere is equally important. Hence, extensive research has been carried out on the development of cost-effective technologies for carbon dioxide capture and techniques to establish hydrogen economy. Hydrogen is a clean energy fuel with a very high specific energy content of about 120MJ/kg and an energy density of 10Wh/kg. However, its potential is limited by the lack of environment-friendly production methods and a suitable storage medium. Conventional hydrogen production methods such as Steam-methane-reformation and Coal-gasification were modified by the inclusion of NaOH. The modified methods are thermodynamically more favorable and can be regarded as near-zero emission production routes. Further, suitable catalysts were employed to accelerate the proposed NaOH-assisted reactions and a relation between reaction yield and catalyst size has been established. A 1:1:1 molar mixture of LiAlH4, NaNH2 and MgH2 were investigated as a potential hydrogen storage medium. The hydrogen desorption mechanism was explored using in-situ XRD and Raman Spectroscopy. Mesoporous metal oxides were assessed for CO2 capture at both power and non-power sectors. A 96.96% of mesoporous MgO (325 mesh size, surface area = 95.08 ± 1.5 m2/g) was converted to MgCO3 at 350°C and 10 bars CO2. But the absorption capacity of 1h ball milled zinc oxide was low, 0.198 gCO2 /gZnO at 75°C and 10 bars CO2. Interestingly, 57% mass conversion of Fe and Fe3O4 mixture to FeCO3 was observed at 200°C and 10 bars CO2. MgO, ZnO and Fe3O4 could be completely regenerated at 550°C, 250°C and 350°C respectively. Furthermore, the possible retrofit of MgO and a mixture of Fe and Fe3O4 to a 300 MWe coal-fired power plant and iron making industry were also evaluated.

Developing effective methods of generating thin metal oxide films are important for sensing and separations applications. An obstacle to device fabrication is controlling the size and spatial orientation of domain level pores while retaining the ability to generate arbitrary device level patterns. Well-ordered hexagonally packed cylindrical pores were created by taking advantage of block copolymer self-assembly followed by selective condensation of silica precursors using supercritical carbon dioxide as the solvent. It was possible to control the pore size by choosing PEO-PPO-PEO (Pluronic® series) triblock copolymers of differing molecular weights. These processes were then incorporated with conventional lithographic techniques to generate patterns on the device scale. The first route involves replacement of the organic acid catalyst with a photoacid generator that restricts acid formation by masking pre-determined regions then exposing to UV light. The second route is similar except that addition of a cross-linking agent limits acid diffusion while reversing the tone of the final pattern. The third route avoids acid diffusion altogether and generates the pattern through reactive ion etching through a sacrificial photoresist. A completely different fourth route was taken and nanoimprint lithography was used to generate sub-micron patterns with alternate block copolymers. The feasibility of the preliminary devices generated in this thesis has been examined through particle diffusion experiments. Samples were soaked in a fluorescent dye then exposed to multiple sizes of gold nanoparticles. Fluorescence quenching was then monitored to determine pore accessibility.

An experimental study of several variants of radius and strut angle of the body centered cubic unit cell was performed to determine the mechanical properties and failure mechanisms of the mesostructure. Quasi static compression tests were performed on an Instron® universal testing machine with a 50kN load cell at 0.2mm/min. The test samples were built using a SLM Solutions 125 selective laser melting machine with 316L stainless steel. Test specimens were based on 5mm cubic unit cells, with a strut diameter 10% of the unit cell size, with skins on top and bottom to provide a cantilever boundary constraint. Specimens were inspected for dimensional accuracy using precision calipers and inspected for morphology using a MicroVu® macroscope. The compressive properties of the mesostructure was compared to the compressive properties of macrostructure. The BCC unit cell behaves significantly different at the boundary layer of a constrained lattice. The failure mode at the boundary is characterized by plastic bending within the microstruts while the non boundary layer cells fail via plastic bending at the node. Manufacturing compensation parameters were determined for part shrinkage and droop. Two predictive numerical models were developed, based on the Gibson-Ashby model of cellular solids, as well as a finite element model. Numerical results did not agree well with the experimental results, indicating that the droop observed on the structures significantly affects the mechanical properties of the overall structure. The 25% radius cubic unit cell and 3^3 lattice withstood the greatest stress of all specimens tested and exhibited nearly ideal plastic deformation behavior.

Rapid battery exchange systems were built for an electric van and pedal assist electric bike as a method of eliminating the need to recharge the vehicles batteries in order to increase the feasibility of using electric propulsion as a method of efficient student transportation. After selecting proper materials it was found that the systems would need a protective coating to ensure consistent operation. 1020 cold rolled steel samples coated with multiple thicknesses of vinyl resin paint, epoxy resin paint, and powder coating were subjected to environmental wear tests in order to determine if the type and thickness of common protective coatings has an effect on the durability of the system over its lifetime. The tests consisted of a 2400 hour extended salt spray test, coating delamination testing, and modified impact testing. The extended salt spray test, delamination test, and deformation tests of the coatings all found that the type of coating and the thickness of the coating to have a significant effect on the measured outputs. The significant effect shown in the deformation test could not determine the proper material without the aid of microscopic studies of the surface geometry change due to the induced deformation. Powder coating the rapid battery exchange systems would result in proper performance if coupled with epoxy paint for repairs. Testing of the Rapid battery exchange system indicated that the use of mechanical aiming was not suitable for the application, a further adaptation of the system indicated that the system may be better suited toward personal bicycles as there was a large increase in transportation efficiency.

<p>A self‐consistent model for non‐partitioning planar ferrite growth from alloyed austenite is developed. The model captures the evolution with time of interfacial contact conditions for substitutional and interstitial solutes. Substitutional element solute drag is evaluated in terms of the dissipation of free energy within the interface, and an estimate is provided for the rate of buildup of the alloying element ‘‘spike’’ in austenite. The transport of the alloying elements within the interface region is modeled using a discrete‐jump model, while the bulk diffusion of C is treated using a standard continuum treatment.</p> <p>The model is validated against ferrite precipitation and decarburization kinetics in the Fe‐Ni‐C, Fe‐Mn‐C, Fe‐Mo‐C, Fe‐Si‐C, Fe‐Cr‐C and Fe‐Cu‐C systems.</p> / Doctor of Philosophy (PhD)

<p>Electrohydrodynamics (EHD) was used to enhance the thermal performance of a latent heat thermal storage cell by reducing the charging time for a given amount of latent heat stored. Paraffin wax, which is an organic dielectric commercially available material was selected as the phase change material (PCM).</p> <p>Electric field was applied into the cell by using 9 electrodes kept at -8 kV in an effort to establish EHD forces inside the PCM. The EHD effect was studied in an originally conduction dominated melting environment. That was achieved by the cell design which promoted unidirectional melting downwards to prevent natural convection from occurring by assuring a thermally stratified molten phase. The target was to study the EHD mechanisms of enhancement with less interfering physics.</p> <p>Melting was studied under constant heat flux boundary condition. The temporal thermal profile of the surface heater and the melt front location were used to assess the EHD effect by comparing it to a 0 kV (no EHD) case.</p> <p>It was found that by using EHD (-8 kV), the time required to melt 7 mm thickness of the PCM can be reduced by 40 % when compared to 0 kV case. Through a four hour experiment time, the amount of molten PCM can be increased by 29 % by using EHD compared to 0 kV. The EHD power consumption was less than 0.17 W which is equivalent to 2.4 % of the thermal energy stored in the PCM.</p> <p>A new phenomena was discovered when applying EHD in the tested cell, which is Solid Extraction, where the solid dendrites within the mushy zone were extracted from the mushy zone into the liquid bulk towards regions of higher electric field.</p> <p>A new criteria was developed to quantify the EHD enhancement level and was called EHD enhancement factor. An enhancement factor up to 13 could be reached by using EHD. The effect of changing the heat flux on the enhancement factor was investigated, and it was found that the enhancement factor decreased by increasing the heat flux.</p> <p>Numerical simulations were performed in an effort to understand the EHD mechanisms of enhancement. The static electric field distribution, the interfacial extraction forces and the body forces acting on suspended dendrites were evaluated. The results of numerical simulations were supported by the high speed imaging and the experimental data to explain the EHD mechanisms of enhancement and the regions where solid dendrites extraction happened.</p> <p>Finally an analytical model was developed to estimate the energy stored in the different components of the tested latent heat storage cell and to estimate the amount of energy lost to the surroundings in order to quantify the accuracy of the experiment and a maximum of 18 % heat loss was estimated.</p> / Master of Applied Science (MASc)

An experimental method was further developed to quantify the anisotropy of multi-site fatigue crack initiation behaviors in high strength Al alloys by four-point bend fatigue testing under stress control. In this method, fatigue crack initiation sites (fatigue weak-links, FWLs) were measured on the sample surface at different cyclic stress levels. The FWL density in an alloy could be best described using a three-parameter Weibull function of stress, though other types of sigmoidal functions might also be used to quantify the relationship between FWL density and stress. The strength distribution of the FWLs was derived from the Weibull function determined by fitting the FWLs vs. stress curve experimentally obtained. As materials properties, the FWL density and strength distribution could be used to evaluate the fatigue crack nucleation behaviors of engineering alloys quantitatively and the alloy quality in terms of FWL density and strength distribution. In this work, the effects of environment, types of microstructural heterogeneities and loading direction on FWLs were all studied in detail in AA7075-T651, AA2026-T3511, and A713 Al alloys, etc. It was also found that FWLs should be quantified as a Weibull-type function of strain instead of stress, when the applied maximum cyclic stress exceeded the yield strength of the tested alloys. In this work, four-point bend fatigue tests were conducted on the L-T (Rolling-Transverse), L-S (Rolling-Short transverse) and T-S planes of an AA7075-T651 alloy plate, respectively, at room temperature, 20 Hz, R=0.1, in air. The FWL populations, measured on these surfaces, were a Weibull-type function of the applied maximum cyclic stress, from which FWL density and strength distribution could be determined. The alloy showed a significant anisotropy of FWLs with the weak-link density being 11 mm-2, 15 mm-2 and 4 mm-2 on the L-T, L-S and T-S planes, respectively. Fatigue cracks were predominantly initiated at Fe-containing particles on the L-T and L-S planes, but only at Si-bearing particles on the T-S plane, profoundly demonstrating that the pre-fractured Fe-containing particles were responsible for crack initiation on the L-T and L-S planes, since the pre-fracture of these particles due to extensive deformation in the L direction during the prior rolling operation could only promote crack initiation when the sample was cyclically stressed in the L direction on both the L-T and L-S planes. The fatigue strengths of the L-T, L-S and T-S planes of the AA7075 alloy were measured to be 243.6, 273.0 and 280.6 MPa, respectively. The differences in grain and particle structures between these planes were responsible for the anisotropy of fatigue strength and FWLs on these planes. Three types of fatigue cracks from particles, type-I: the micro-cracks in the particles could not propagate into the matrix, i.e., type-II: the micro-cracks were fully arrested soon after they propagated into the matrix, and type-III: the micro-cracks became long cracks, were observed in the AA7075-T651 alloy after fatigue testing. By cross-sectioning these three-types of particles using Focused Ion Beam (FIB), it was found that the thickness of the particles was the dominant factor controlling fatigue crack initiation at the particles, namely, the thicker a pre-fractured Fe-containing particle, the easier it became a type-III crack on the L-T and L-S planes. On the T-S plane, there were only types-I and III Si-bearing particles at which crack were initiated. The type-I particles were less than 6.5 μm in thickness and type-III particles were thicker than 8.3 μm. Cross-sectioning of these particles using FIB revealed that these particles all contained gas pores which promoted crack initiation at the particles because of higher stress concentration at the pores in connection with the particles. It was also found that fatigue cracks did not always follow the any specific crystallographic planes within each grain, based on the Electron Backscatter Diffraction (EBSD) measurement. Also, the grain orientation did not show a strong influence on crack initiation at particles which were located within the grains. The topography measurements with an Atomic Force Microscope (AFM) revealed that Fe-containing particles were protruded on the mechanically polished surface, while the Si-bearing particles were intruded on the surface, which was consistent with hardness measurements showing that Si-bearing particles were softer (4.030.92 GPa) than Fe-containing ones (8.9 0.87 GPa) in the alloy. To verify the 3-D effects of the pre-fractured particles on fatigue crack initiation in high strength Al alloys, rectangular micro-notches of three different types of dimensions were fabricated using FIB in the selected grains on the T-S planes of both AA2024-T351 and AA7075-T651 Al alloys, to mimic the three types of pre-fractured particles found in these alloys. Fatigue testing on these samples with the micro-notches verified that the wider and deeper the micro-notches, the easier fatigue cracks could be initiated at the notches. In the AA2024-T351 samples, cracks preferred to propagate along the {111} slip plane with the smallest twist angle and relatively large Schmid factor. These experimental data obtained in this work could pave a way to building a 3-D quantitative model for quantification of fatigue crack initiation behaviors by taking into account the driving force and resistance to short crack growth at the particles in the surface of these alloys.

Abstract An experimental method was developed that demonstrated the size effects in forming thin sheet metals, and a finite element model was developed to predict the effects demonstrated by the experiment. A universal testing machine (UTM) was used to form aluminum and copper of varying thicknesses (less than 1mm) into a hemispherical dome. A stereolithography additive manufacturing technology was used to fabricate the punch and die from a UV curing resin. There was agreement between the experimental and numerical models. The results showed that geometric size effects were significant for both materials, and these effects increased as the thickness of the sheets decreased. The demonstration presents an inexpensive method of testing small-scale size effects in forming processes, which can be altered easily to produce different shapes and clearances.