This research work presents the first comprehensive study on nanocrystalline materials produced in bulk quantities using a novel continuous electrodeposition process. A series of nanocrystalline Ni and Ni-Fe alloy continuous foils were produced and an intensive investigation into their structure and various properties was carried out. High-resolution transmission electron microscopy (HR-TEM) revealed the presence of local strain at high and low angle, and twin boundaries. The cause for these local strains was explained based on the interpretation of non-equilibrium grain boundary structures that result when conditions of compatibility are not satisfied. HR-TEM also revealed the presence of twin faults of the growth type, or “growth faults”, which increased in density with the addition of Fe. This observation was found to be consistent with a corresponding increase in the growth fault probabilities determined quantitatively using X-ray diffraction (XRD) pattern analysis. Hardness and Young’s modulus were measured by nanoindentation. Hardness followed the regular Hall-Petch behaviour down to a grain size of 20 nm after which an inverse trend was observed. Young’s modulus was slightly reduced at grain sizes less than 20 nm and found to be affected by texture. Microstrain based on XRD line broadening was measured for these materials and found to increase primarily with a decrease in grain size or an increase in intercrystal defect density (i.e., grain boundaries and triple junctions). This microstrain is associated with the local strains observed at grain boundaries in the HR-TEM image analysis. A contribution to microstrain from the presence of growth faults in the nanocrystalline Ni-Fe alloys was also noted. The macrostresses for these materials were determined from strain measurements using a two-dimensional XRD technique. At grain sizes less than 20 nm, there was a sharp increase in compressive macrostresses which was also owed to the corresponding increase in intercrystal defects or interfaces in the solid.

This research work presents the first comprehensive study on nanocrystalline materials produced in bulk quantities using a novel continuous electrodeposition process. A series of nanocrystalline Ni and Ni-Fe alloy continuous foils were produced and an intensive investigation into their structure and various properties was carried out. High-resolution transmission electron microscopy (HR-TEM) revealed the presence of local strain at high and low angle, and twin boundaries. The cause for these local strains was explained based on the interpretation of non-equilibrium grain boundary structures that result when conditions of compatibility are not satisfied. HR-TEM also revealed the presence of twin faults of the growth type, or “growth faults”, which increased in density with the addition of Fe. This observation was found to be consistent with a corresponding increase in the growth fault probabilities determined quantitatively using X-ray diffraction (XRD) pattern analysis. Hardness and Young’s modulus were measured by nanoindentation. Hardness followed the regular Hall-Petch behaviour down to a grain size of 20 nm after which an inverse trend was observed. Young’s modulus was slightly reduced at grain sizes less than 20 nm and found to be affected by texture. Microstrain based on XRD line broadening was measured for these materials and found to increase primarily with a decrease in grain size or an increase in intercrystal defect density (i.e., grain boundaries and triple junctions). This microstrain is associated with the local strains observed at grain boundaries in the HR-TEM image analysis. A contribution to microstrain from the presence of growth faults in the nanocrystalline Ni-Fe alloys was also noted. The macrostresses for these materials were determined from strain measurements using a two-dimensional XRD technique. At grain sizes less than 20 nm, there was a sharp increase in compressive macrostresses which was also owed to the corresponding increase in intercrystal defects or interfaces in the solid.

Estimating the in situ mechanical properties of sediments containing gas hydrates from seismic or log data is essential for evaluating the risks posed by mechanical failure during drilling, completions, and producing operations. In this paper, a method is presented for constructing correlations between the mechanical properties of gas hydrate bearing sediments and geophysical data. A theory based on micromechanics models was used to guide the selection of parameters that govern the physical behavior of sediments. A set of nondimensionalized relations between elastoplastic properties and those that could be inferred from log or seismic data was derived. Using these relations, a correlation for the Young’s modulus was constructed for sands with methane and THF hydrate using data from a wide variety of sources. It was observed that the correlation did not fit data obtained from samples with high THF hydrate saturations, due possibly to the existence of cohesive mechanisms that operate in such regimes.

Geopolymerization has been considered as a new technology to replace the ordinary Portland cement in construction industry. It provides an option to manage the industry waste and byproducts like fly ash, mine tailings. At the same time, the CO₂ emissions can be reduced about 80% compared to that of ordinary Portland cement. The present research includes three main parts. First part is applying mine tailings as construction materials using geopolymerization method. The study is focused on efficiently activating mine tailings, reducing alkali consumption, decreasing curing time and improving compressive strength. We investigate the activation temperature effects, the impacts of additives and effects of forming pressures. The results show that a 40 MPa unconfined compressive strength (UCS) can be achieved with the geopolymerization samples after mine tailings are activated by sodium hydroxide at 170°C for 1 hour with the addition of calcium hydroxide and alkali dissolved aluminium oxide, further compressed with a 10 MPa forming pressure and finally cured at 90°C for 3 days. To elucidate the mechanism for the contribution of additives to geopolymerization, microscopic and spectroscopic techniques including scanning electron microscopy/ energy-dispersive X-ray spectroscopy (SEM/EDX), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy are used to investigate the micro/nanostructure and the elemental and phase composition of geopolymerization specimens. The stress-strain behavior was also characterized. The results shows that the mechanical behavior is similar with that of concrete and the dynamic modulus is 22 GPa, which is comparable with that of concrete. The Young's modulus of geopolymer product was also calculated and the value is in the range of 2.9 to 9.3 GPa. The findings of the present work provide a novel method for the geopolymerization of mine tailings as construction materials. Second section is applying fly ash as a high strength water-resistant construction material. Through the present investigation, a procedure has been studied. The experiment results indicate that the concentration of NaOH, water content, and curing condition can significantly affect the mechanical property of geopolymer matrix. At the same time, the chemical composition, especially the Si/Al ratio and calcium content, is also an important factor during geopolymerization. XRD results show that the amorphous feature can be observed for both high and low calcium fly ash. It is the key of the success of geopolymerizaton due to its high reactivity. XRD, FTIR and SEM tests were performed to study how experiment conditions and the properties of fly ash affect geopolymerization. The obtained compressive strength of the geopolymerization product can reach above 100 MPa. The stress-strain behavior was also characterized. The results shows that the dynamic modulus is 36.5 GPa. The product obtained from the present work shows very high water resistance without losing any compressive strength even after a one month soaking time. Third part is applying the mixture of class C fly ash and mine tailings as construction materials. Through the present investigation, a protocol has been set up. The experiment results of the present work also help set up the working conditions such as activation temperature and time, the concentration of NaOH, the addition of Ca(OH)₂, forming pressure, mine tailing to class C fly ash weight ratio, curing temperature and curing time. To elucidate the mechanism for the contribution of additives to geopolymerization, microscopic and spectroscopic techniques such as SEM/EDX, X-ray diffraction and FTIR spectroscopy were used to investigate the micro/nanostructure and the elemental and phase composition of geopolymerization composite. The obtained compressive strength of the geopolymerization product can reach above 60 MPa. The stress-strain behavior of the geopolymer matrix of the mixture of mine tailing and fly ash were also characterized and the results show that the mechanical behavior is similar to that of concrete with a 24 GPa dynamic modulus. The Young's modulus of geopolymer product was also calculated and the value is in the range of 4.0 to 13.5 GPa. The findings of the present work provide a novel method for the geopolymerization of the mixture of mine tailings and class C fly ash as construction materials, such as bricks for construction and road pavement.

In the TRISO (tristructural isotropic) coated fuel particle used in the High Temperature Reactor, the most important layer is a silicon carbide layer which acts as a pressure vessel. In this study, we have focused our study on the investigation of the Young’s modulus, hardness, residual stress, and fracture toughness of the SiC layer. Moreover, microstructures and impurities in silicon carbide were characterised and then related to both Young’s modulus and hardness of the SiC layer. Both nanoindentation and micro-indentation were used to determine Young’s modulus and hardness of the SiC. Raman spectroscopy, X-ray diffraction, and scanning electron microscopy techniques were used to examine impurities, phases and microstructure of silicon carbide layers, respectively. Young’s modulus was measured at different positions of a polished surface of the SiC with different CVD growth and crystal orientations. With help from the finite element modelling, it has been found that Young’s modulus of the SiC is dependent on the grain orientation of the SiC. Mechanical properties of silicon carbide are affected by the presence of excess silicon, excess carbon, stacking faults, texture, grain size, property of grain boundary. The effect of these factors on Young’s modulus and hardness, are investigated with the orthogonal analysis. The analysis concludes that the most important factor on Young’s modulus is texture while the most significant factor on hardness is grain boundary. Grain size is secondarily important factor to affect hardness. Stacking faults and impurities almost have no influence on Young’s modulus and hardness. The residual stress in the silicon carbide layer was measured based on the peak shift in Raman spectra of the SiC and is in a range of 150-300 MPa. Fracture resistance in the radial direction of the SiC layer is larger than those in the circumferential direction. The difference is controlled by the layer-like structure of the SiC coating.

Next-generation batteries with improved microstructure and performance are on their way to meet the market demands for high-energy and power storage systems. Among different types of batteries, Li-ion batteries remain the best choice for their high energy density and long lifetime. There is a constant but slow improvement in Li-ion batteries by developing new materials and fabrication techniques. However, further improvements are still needed to meet government and industry goals for cost, cycling performance, and cell lifetime. A fundamental understanding of particle-level interactions can shed light on designing new porous electrodes for high-performance batteries. This is a complex problem because electrodes have a multi-component, multi-phase microstructure made through multiple fabrication processes (i.e., mixing, coating, drying, and calendering). Each of these processes can affect the final microstructure (particle and pore locations) differently. This work seeks to understand the porous microstructure evolution of Li-ion electrodes during the drying and calendering fabrication processes by a combination of modeling and experimental approaches. The goal is to understand the mechanisms by which the electrode components and fabrication processes determine the battery microstructure and subsequent cell performance. A multi-phase smoothed particle (MPSP) model has been developed on a publically available simulation platform known as LAMMPS. This model was used to simulate particle-level interactions and predict the mechanical and transport properties of four fabricated electrodes (i.e. a graphite anode and three traditional metal oxide cathodes). One challenge was to include different electrode components and their interactions and relate them to physical properties like density and viscosity that can be measured experimentally. Another challenge was to generate required electrode property data for model validation, which in general was not found in the literature. Therefore, a series of experiments were conducted to provide that information, namely slurry viscosity, electronic conductivity, porosity, tortuosity, elastic modulus, and electrode crosssections. Understanding these properties has value to the battery community independent of their use in this study. The MPSP model helps us explain observed transport heterogeneity after calendering but brings up new questions about the drying process that have not been addressed in previous works. Therefore, the drying fabrication step was studied experimentally in more detail to fill this knowledge gap and explain our simulation results. The MPSP model can also be used as a predictive tool to explore the design space of Li-ion electrodes where conducting the actual experiments is very challenging. For example, the distinct effect of particle size, shape, orientation, and stiffness on electrode transport and mechanical properties are difficult to determine independently, and therefore this model is an ideal tool to understand the effect of these properties. The final model, which is publically available, could be used with adjustments by future workers to test new materials, fabrication processes, or electrode design (e.g., a multi-layered structure).

M. Tech. (Department of Metallurgical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / Elemental titanium (Ti), niobium (Nb), zirconium (Zr), and iron (Fe) powders were used to fabricate four near-β alloys with non-toxic of composition Ti-34Nb-25Zr, Ti-34Nb-25Zr-0.4Fe, Ti-34Nb-25Zr-1.2Fe, and Ti-34Nb-25Zr-2Fe (wt. %) (TNZ and TNZF) using spark plasma sintering (SPS) of nano-crystalline powders attained by high energy ball milling. The fabricated alloys were compared to Ti-34Nb-25Zr (used as a benchmark alloy in this study) and comparison was made with the commercially used Ti base alloys produced either by conventional methods or powder metallurgy. The powder mixtures were milled for 5 hours using a Simoloyer high energy ball mill with a ball to powder ratio of 10:1 and a rotational speed of 1000 rpm. This was followed by sintering the mechanically alloyed powders at 1100 ºC for 10 minutes with a pressure of 50 MPa and a heating rate of 100 ºC/min using an H-HP D25 spark plasma sintering furnace (FCT System, Germany). The powders were characterised for particle size and crystal structure using SEM and XRD. The consolidated components were characterised with regards to density, microstructure, mechanical properties. The electrochemical behaviour of the alloys was investigated using a Digi Ivy DY2300 series potentiostat. Three corrosion medium, Sodium chloride (NaCl), phosphate buffered saline solution (PBS) and Dulbecco’s modified eagle’s medium that mimic the conditions in the human body were used. Mouse myoblast cell line (C2C12) was used to investigate the biocompatibility of the sintered alloys in 1010x5 mm specimens using standard colorimetric assay MTT. Both electrochemical and biocompatibility test were conducted in triplicates and the results compared with that of the benchmark. Results of mechanical alloying of powder mixtures demonstrated an inhomogeneous structure. Milling for 5 hours resulted in agglomeration of small Fe and Zr particles. Milling for 3 hours resulted in a better distribution of elements compared to longer milling times. Therefore, sintering powders milled for 3 hours would have yielded better results. The densification results were acceptable and ranged between 97-99% of theoretical densities. Although some porosity was observed, especially on the un-etched microstructure. An insignificant decrease in density was observed when 1.2 (wt. %) Fe was added. The sintered samples had microstructures which were not homogenous. However, the addition of Fe yielded a more homogeneous microstructure compared to the one with less Fe. Therefore, TNZF with 2 (wt. %) Fe had a more homogenous microstructure. Sintering at 1100 ºC resulted in undissolved niobium and titanium which were observed in the microstructure as dark and white areas. The hardness of the TNZF alloys were comparable and lied between 373 and 432 Hv. These hardness values are higher than other similar titanium-based alloys fabricated using conventional methods. The addition of Fe to TNZ showed an insignificant decrease in hardness. The addition of Fe was found to decrease the Young’s Modulus of TNZ from 119.1 to 80 GPa with an addition of 2 wt.% Fe. However, an unacceptable reduction (230.91 to 158.2 MPa) in strength was also noticed. Pseudo passivation was observed when the alloys were immersed in 0.9 % Sodium Chloride (NaCl) which could be attributed to the inhomogeneity in the microstructure. The possibility of pitting corrosion was also observed. The alloy containing 2 Fe (wt.%) was found to be more corrosion resistant than the other alloys. The TNZF alloys exhibited better corrosion resistance in 0. 9% NaCl compared to phosphate buffered solution (PBS) and DMEM. The corrosion behaviour in PBS and DMEM cannot clearly be explained from the graphs. The morphology of the corroded samples was almost the same for all the alloys in different corrosion media. The microstructures showed pits which could have been from the pores that acted as initiation sites for pitting. In cell culture for 1 and 7 days, the cell viability for TNZF alloys was greater than that of the control group (TNZ). A significant decrease in cell viability for TNZF was observed in cell culture for 4 days. The addition of Fe on TNZ do not cause toxic effects and show good cell adhesion, indicating in-vitro cytocompatibility. The greatest cell viability of 102±3.0 % for Ti-34Nb-25Zr-2Fe. The analysis of cell morphology indicated good cell-substrate interaction. The TNZF alloys developed in this study can be suitable candidates for orthopaedic implant application due to their low Young’s modulus, corrosion resistance and superior biocompatibility. However, the strength needs significant improvement. The advantage of this biomaterial, when compared to commercial alloys, is the absence of cytotoxicity elements such as Al and V.

No description available.

Poly(N-isopropyl-acrylamide) (PNIPAM) is a thermoresponsive polymer with a wide range of biological applications, including drug delivery, biosensing, and tissue engineering. The tunability of the structural and mechanical properties of PNIPAM makes it particularly at- tractive in emulating cell environments and dynamic cytoskeletal deformations. This thesis discusses PNIPAM's properties and applications in different forms i.e., solution, brushes, hydrogels, and surface patterned hydrogels, with specific focus on lithographically patterned substrates coated with PNIPAM films. The scaffolds are investigated for structural and me- chanical responses to thermally driven changes in the PNIPAM hydration states using atomic force microscopy (AFM). AFM measurements on our lithographically patterned substrates show that the substrate pattern and coating method enable the fabrication of scaffolds with different topographic and mechanical properties across a wide thermal range. Importantly, these scaffolds exhibit variations in both lateral topography and Young's modulus, rendering them well suited for investigations of differential mechanical stresses experienced by cells and cell membranes. / Master of Science / Poly(N-isopropyl-acrylamide) (PNIPAM) is a polymer which can change its water absorption depending on the temperature of its aqueous environment. It transitions from a swollen state at room temperature to a collapsed state at around 32 °C. These thermally tunable properties make PNIPAM an attractive candidate in a variery of applications, including biomedical and biophysical applications. In this thesis, PNIPAM is coated on lithographically patterned substrates to emulate the cellular cytoskeleton. Atomic force microscopy (AFM) measurements are performed to measure the topography and mechanical properties of the fabricated scaffolds. The results show that the coating method and the features of the used substrate allow the fabrication of different surface topographies with biologically relevant mechanics.

This study demonstrates that the surface motility of the bacterium Pseudomonas aeruginosa is dependent on the surface chemistry of the underlying substrate. In particular, cells on hydrophobic polydimethylsiloxane (PDMS) have a speed that is on average 38% greater than on hydrophilic PDMS. These results were obtained using time-lapse microscopy of bacteria exposed to continuously flowing tryptic soy broth growth medium at 37 ⁰C. Not only are the mean speeds different, the distributions of speeds are also different: on the hydrophobic substrate, a smaller proportion of bacteria move by less than about one body-length (~3 µm) in 60 minutes. In addition, the surface chemistry affects the orientation of the cells: there is a greater fraction of "walking" bacteria on the hydrophobic surface. Sensitivity to the substrate surface chemistry occurs despite the presence of a complex mix of substances in the growth medium and offers hope that surface chemistry can be used to tune motility and the progression to biofilm formation. Additionally, the effect of reducing the near-surface Young's modulus of the PDMS from 7000 to 70 kPA is investigated. For the lower modulus material, there is an increase in the likelihood of a bacterium executing sudden, high angle turns. This is evident in images with a framerate of one frame per 0.22s. However, the impact of these turns is averaged out over longer times such that the mean speed over periods of more than about one minute is the same for bacteria on both the high and the low modulus materials. Consequently, except over very short time intervals, Young's modulus in the surface region is not effective as a means of modulating motile behavior. / Master of Science / This study demonstrates that the ability of the bacterium Pseudomonas aeruginosa to move on a solid surface is dependent on the surface chemistry of the underlying substrate. In particular, cells on hydrophobic polydimethylsiloxane (PDMS) have a speed that is on average 38% greater than on hydrophilic PDMS. These results were obtained using time-lapse microscopy of bacteria exposed to continuously flowing growth medium at 37 ⁰C. Not only are the mean speeds different, the distributions of speeds are also different: on the hydrophobic substrate, a smaller proportion of bacteria move by less than about one body-length (~3 µm) in 60 minutes. In addition, the surface chemistry affects the orientation of the cells: there is a greater fraction of vertically-oriented bacteria on the hydrophobic surface. Additionally, the effect of reducing the stiffness of the PDMS from 7000 to 70 kPA is investigated. For the less stiff material, there is an increase in the likelihood of a bacterium executing sudden, high angle turns. This is evident in images with a framerate of one frame per 0.22s. However, the impact of these turns is averaged out over longer times such that the mean speed over periods of more than about one minute is the same for bacteria on both the high and the low stiffness materials. Consequently, except over very short time intervals, stiffness in the surface region is not effective as a means of changing patterns of surface-bound P. aeruginosa movement.