Yttria Partially Stabilized Zirconia (Y-PSZ) plasma-sprayed coatings are widely used in turbine engines as thermal barrier coatings. However, in diesel engines Y-PSZ TBCs have not met with wide success. To reach the desirable temperature of 850-900˚C in the combustion chamber from the current temperature of 400-600˚C, a coating with a thickness of approximately 1mm is required. This introduces different considerations than in the case of turbine blade coatings, which are on the order of 100µm thick. Of the many factors affecting the durability and failure mechanism of TBCs, in service and residual stresses play an especially important role as the thickness of the coating increases. For decreasing the residual stress in the system, a multi-layer coating is helpful. The design of a multilayer coating employing relatively low cost materials with complementary thermal properties is described. Numerical models were used to describe the residual stress after deposition and under operating conditions for a multilayer coating that exhibited the desired temperature gradient. Results showed that the multilayer coating had a lower maximum stress under service conditions than a conventional Y-PSZ coating. Model validation with experiments showed a good match between the two.

Two methods for refining metallurgical grade silicon to solar grade silicon have been investigated. The first method involved the reduction of impurities from metallurgical grade silicon by high temperature vacuum refining. The concentrations of analyzed elements were reduced several times. The main steps in the second refining method include alloying with copper, solidification, grinding and heavy media separation. A metallographic study of the Si-Cu alloy showed the presence of only two microconstituents, mainly pure silicon dendrites and the Cu3Si intermetallic. SEM analysis showed a distinct boundary between the silicon and the Cu3Si phases, with a large concentration of microcracks along the boundary, which allowed for efficient separation. After alloying and grinding, a heavy media liquid was used to separate the light silicon phase from the heavier Cu3Si phase. Cu3Si residues together with the remaining impurities were found to be located at the surface of the pure silicon particles, and should be efficiently removed by acid leaching. Thirty elements were analyzed by the Inductively Coupled Plasma Mass Spectrometry (ICP) chemical analysis technique. ICP revealed a several times higher impurity level in the Cu3Si intermetallic than in the pure silicon; furthermore, the amounts of 22 elements in the refined silicon were reduced below the detection limit where the concentrations of 7 elements were below 1ppmw and 6 elements were below 2ppmw. The results showed that the suggested method is efficient in removing impurities from metallurgical grade silicon with great potential for further development.

Nanocrystalline materials have generated immense scientific interest, primarily due to observations of significantly enhanced strength and hardness resulting from Hall-Petch grain size strengthening into the nano-regime. Unfortunately, however, most previous studies have been unable to present material strength measurements using established tensile tests because the most commonly accepted tensile test protocols call for specimen geometries that exceeded the capabilities of most nanocrystalline material synthesis processes. This has led to the development of non-standard mechanical test methodologies for the evaluation of miniature specimens, and/or the persistent use of hardness indentation as a proxy for tensile testing. This study explored why such alternative approaches can be misleading and revealed how reliable tensile ductility measurements and material strength information from hardness indentation may be obtained. To do so, an electrodeposition-based synthesis method to produce artifact-reduced specimens large enough for testing in accordance with ASTM E8 was developed. A large number of 161 samples were produced, tested, and the resultant data evaluated using Weibull statistical analysis. It was found that the impact of electroforming process control on both the absolute value and variability of achievable tensile elongation was strong. Tensile necking was found to obey similar processing quality and geometrical dependencies as in conventional engineering metals. However, unlike conventional engineering metals, intrinsic ductility (as measured by maximum uniform plastic strain) was unexpectedly observed to be independent of microstructure over the grain size range 10-80nm. This indicated that the underlying physical processes of grain boundary-mediated damage development are strain-oriented phenomena that can be best defined by a critical plastic strain regardless of the strength of the material as a whole. It was further shown that the HV = 3•σUTS expression is a reliable predictor of the relationship between hardness and strength for electrodeposited nanocrystalline materials, provided the material is ductile enough to sustain tensile deformation until the onset of necking instability. The widely used relationship HV = 3•σY was found to be inapplicable to this class of materials owing to the fact that they do not deform in an “ideally plastic” manner and instead exhibit plastic deformation that is characteristic of strain hardening behaviour.

Traditional blowing agents (e.g., hydrochlorofluorocarbons) in plastic foaming processes has been phasing out due to environmental regulations. Plastic foaming industry is forced to employ greener alternatives (e.g., carbon dioxide, nitrogen), but their foaming processes are technologically challenging. Moreover, to improve the competitiveness of the foaming industry, it is imperative to develop a new generation of value-added plastic foams with cell structures that can be tailored to different applications. In this context, the objective of this thesis is to achieve a thorough understanding on cell nucleation and growth phenomena that determine cell structures in plastic foaming processes. The core research strategy is to develop innovative visualization systems to capture and study these phenomena. A system with accurate heating and cooling control has been developed to observe and study crystallization-induced foaming behaviors of polymers under static conditions. The cell nucleation and initial growth behavior of polymers blown with different blowing agents (nitrogen, argon and helium, and carbon dioxide-nitrogen mixtures) have also been investigated in great detail. Furthermore, two innovative systems have been developed to simulate the dynamic conditions in industrial foaming processes: one system captures a foaming process under an easily adjustable and uniform extensional strain in a high temperature and pressure environment, while the other achieves the same target, but with shear strain. Using these systems, the extensional and shear effects on bubble nucleation and initial growth processes has been investigated independently in an isolated manner, which has never been achieved previously. The effectiveness of cell nucleating agents has also been evaluated under dynamic conditions, which have led to the identification of new foaming mechanisms based on polymer-chain alignment and generation of microvoids under stress. Knowledge generated from these researches and the wide range of future studies made possible by the visualization systems will be valuable to the development of innovative plastic foaming technologies and foams.

Secondary sludge is an essential part of biosolids produced through the waste treatment plant of paper mills. Globally paper mills generate around 3.0 million ton of biosolids and in the absence of beneficial applications, the handling and disposal of this residual biomass poses a serious environmental and economic proposition. Secondary paper sludges were investigated in this work for recovery of proteins and their use as wood adhesive. After identifying extracellular polymeric substances as adhesion pre-cursors through analytical techniques, studies were carried out to optimize protein recovery from SS and its comprehensive characterization. A modified physicochemical protocol was developed to recover protein from secondary sludge in substantial quantities. The combined effect of French press and sonication techniques followed by alkali treatment resulted in significant improvement of 44% in the yield of solubilized protein compared to chemical methods. The characterization studies confirmed the presence of common amino acids in recovered sludge protein in significant quantities and heavy metal concentration was reduced after recovery process. The sodium dodecyl sulfate polyacrylamide gel electrophoresis analysis revealed the presence of both low and high molecular weight protein fractions in recovered sludge protein. After establishing the proof-of-concept in the use of recovered sludge protein as wood adhesive, the bonding mechanism of protein adhesives with cellulose substrate was further elucidated in a complementary protein-modification study involving soy protein isolate and its glycinin fractions. The results of this study validated the prevailing bonding theories by proving that surface wetting, protein structure, and type of wood play important role in determining final adhesive strength. Recovered sludge protein was also investigated for its compatibility to formulate hybrid adhesive blends with formaldehyde and bio-based polymers. Apart from chemical cross-linking, the synergy of adhesive blends was evaluated through classical rule-of-mixture. The findings of this study warrants further investigation concerning other potential uses of recovered sludge protein, especially as food supplements and economic implications.

An electrochemical double-layer capacitor (EDLC) is a potential buffer for current power and energy supply. In this work, activated carbon derived from fluid coke as a brand new electrode material was studied due to its high specific surface area (SSA) and large portion of mesopores. A suitable electrode material formula, current collector, and cell configuration were investigated to fabricate a testable system and ensure the reproducibility of measurements. Cyclic voltammetry (CV) and constant current charge/discharge (CD) techniques were used to characterize the performance of the electrode material, as well as to study its fundamental behaviour. A new procedure was established for quantifying the capacitance (Cc) of EDLC from CV which isolates the effect of internal resistance on the measured capacitance (CM). The specific capacitance of single electrode made of activated carbon (~1900 m2/g) with approximately 80% mesopores and macropores was able to reach 180 F/g at scan rate of 0.5mV/s.

Starch-derived bioplastics are an inexpensive, renewable and environmentally-friendly alternative to traditional petroleum-based plastics. Proteins secreted by Ophiostoma ulmi, were investigated for their application in bioplastic product. Proteins were isolated from fungal cultures by anion exchange chromatography and used to treat starch. Subsequently, plastic films were generated by solution casting, with glycerol as plasticizer. Tensile strength of the films was found to increase significantly compared to the control. The relative water holding capacity of the treated starch also decreased dramatically. Attempts to identify fungal proteins by MALDI-TOF MS/MS did not result in positive matches, mainly due to lack of fungal sequence information. Additionally, the effect of non-specific proteins resulted in a modest increase in tensile strength and a slightly greater effect on water absorption. Proteins secreted by O. ulmi were therefore implicated in improving properties of starch-based plastics. Investigation into the role of an extracellular polysaccharide is also suggested.

High strength-to-weight nanocrystalline alloy enabled conductor (NEC) prototypes were successfully developed by reinforcing an oxygen-free copper core material with electrodeposited cobalt phosphorus (CoP) coatings. A rule of mixtures approach was utilized to design the NEC prototypes to meet materials performance indices. Three unique NEC prototypes were produced with CoP coatings composed of alternating nanocrystalline (11 nm) and coarse-grained layers. The tensile properties were dependant on the coating microstructures, with tensile strengths of 1000 MPa, 970 MPa, and 900 MPa, respectively, and corresponding tensile elongations of 4.6%, 6.1%, and 10%, respectively. The electrical conductivity of the NEC prototypes was ~58 %IACS (resistivity of ~2.96 µΩ-cm). The rule of mixtures approach effectively predicted the tensile strength and conductivity. The NEC samples were significantly stronger than the incumbent high-strength aerospace conductor material, Be-Cu alloy CS95, which exhibits a tensile strength of only 655 MPa and conductivity of 63 %IACS.

Rosiglitazone (RSG) is an insulin-sensitizing drug used to treat Type 2 Diabetes Mellitus (T2DM). Clinical trials show that women taking RSG experience more limb fractures than patients taking other T2DM drugs. The purpose of this study is to understand how RSG (3mg/kg/day and 10mg/kg/day) and the bisphosphonate alendronate (0.7mg/kg/week) alter bone quality in the male, female and female ovariectomized (OVX) Zucker fatty rat model over a 12 week period. Bone quality was evaluated by mechanical testing of cortical and trabecular bone. Microarchitecture, bone mineral density (BMD), cortical bone porosity, bone formation/resorption and mineralization were also measured. Female OVX RSG10mg/kg rats had significantly lower vertebral BMD and compromised trabecular architecture versus OVX controls. Increased cortical porosity and decreased mechanical properties occurred in these rats. ALN treatment prevented these negative effects in the OVX RSG model. Evidence of reduced bone formation and excess bone resorption was detected in female RSG-treated rats.

Multi-walled carbon nanotubes (MWCNTs) were successfully coated with two different pseudocapacitive polyoxometalates (POMs) (SiMo12O40-4 (SiMo12) and PMo12O40-3 (PMo12)) via “Layer-by-Layer” deposition. Even with merely a “single-layer” of POM, the modified nanotubes exhibited more than 2X increase in capacitance compared with that of bare nanotubes. To further improve their electrochemical performances, the deposition sequence of the POM layers was adjusted to form “alternate layer” coating to modify MWCNT. A synergistic effect on the capacitance and kinetics was observed with the alternate layer coatings. X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) also proved the successful coating of POMs on MWCNTs. The potential-pH relationship provided important insights in terms of the deposition mechanism and suggested that the bottom layer close to the electrode substrate was the dominating layer in alternate layer coated MWCNT electrodes.