This study concerns the characterization of platinum nickel (PtNi) and platinum vanadium (PtV) near-surface alloys (NSAs) for use as improved catalysts in proton exchange membrane hydrogen fuel cells. The need for this study arose in order to further understand the principles behind the predicted catalytic properties of NSAs, to fabricate them and to characterize them experimentally. Two groups of NSAs were fabricated, namely PtNi and PtV. Pt was used as the parent metal while Ni and V were used as the solute/near surface constituents. Within these groups of pt with Ni or V, variations in coating thickness and heat treatments were used to attempt to fabricate the NSA structure. Surface profile analysis was carried out using profilometry and light microscopy. These techniques showed that surfaces were not always of a 100% mirror finish and that deposited coatings were not stable and were prone to peeling especially with coatings of greater than one layer. Elemental analysis was performed by employing energydispersive x-ray spectroscopy (SEM-EDS), proton induced x-ray emission (PIXE) and Rutherford backscattering spectrometry (RBS). These techniques helped verify the presence of the thin deposited coatings whilst also highlighting the presence of contaminants in the form of iron, manganese and chromium. Tafel Plot analysis was used to gather electrochemical data for the NSAs. In this regard, the hydrogen reduction (evolution) reaction was analyzed with the exchange current density extracted experimentally therefrom. This technique confirmed that Pt is indeed a superior catalyst, especially compared to pure Ni and V. It showed that ebeam deposition did not create coated systems which were suitable for Tafel analysis. It also illustrated that deaeration via nitrogen gas was not always effective with trace oxygen sometimes being present in the purge gas, resulting in contaminant oxygen reduction distorting the electrochemical results. Ultimately, electron-beam deposition proved to be inefficient in fabricating stable coatings for catalysis, with the coatings possibly not being adequately thin to mimic the NSA structure. This, coupled with trace oxygen reduction, prevented effective analysis of NSA catalytic properties.

It has been well established that most fatigue cracks initiate from stress concentration sites found on the surfaces of components subject to cyclic fatigue loading. The introduction of residual compressive stresses into the surface layers of components, through various means including shot peening and laser shock peening, can result in local residual compressive stresses which provide a resistance to both crack initiation and propagation, thus leading to an increase in the fatigue life of the components. The effects of both laser shock peening (LSP) and conventional shot peening (SP) on the fatigue properties of both 7075-T6 and 7075-T0 aluminium round bar test specimens were investigated and compared by means of cyclic 3-point bend fatigue testing. This investigation focused on the role that the peening induced microstructure, surface morphology and hardness had on the fatigue life of the test specimens. It was found that both the laser shock peening and shot peening processes substantially increased the fatigue lives compared to unpeened AA7075-T6. The laser shock peening process more than doubled the fatigue life of the specimens and the shot peening process increased the fatigue life by approximately 1.6×. No discernible hardening effects could be determined in the laser shock peened specimens. However, the shot peening process resulted in a distinct hardened region within the surface layers of the AA7075-T6 specimens which was attributed to the longer pressure duration of the shot peening process which results in greater plastic deformation. It was also shown that polishing the shot peened and laser shock peened specimens after their respective peening procedures resulted in a significant increase in fatigue life. Polishing after peening resulted in a 3.4× fatigue life increase in the shot peened test specimens (T6 condition) and a 5.4× fatigue life increase in the laser shock peened test specimens (T6 condition). This result highlights the role that surface roughness plays in component fatigue life. Furthermore, the increase in the average fatigue life of the polished test specimens shows that the depth of the residual compressive stresses induced by the peening processes were deep enough to allow for surfaces layers to be removed from the test specimens without any detrimental effect to the overall average fatigue life of the components. The result also suggests that the magnitudes of the residual stresses induced by the laser shock peening process being greater than those of the shot peening process. The main difference between the peening treatments was demonstrated as originating from the surface roughening effects of the two peening procedures. The laser shock peening process only slightly increased the surface roughness of a polished AA7075-T6 test specimens. The shot peening process severely affected the surface roughness of the test specimens, creating many potential crack initiation sites. The AA7075-O test specimens (annealed) showed no overall improvement in their fatigue life, regardless of the mechanical treatment received. The increased ductility of the specimens during the 3-point bending fatigue process led to stress relieving of the peening induced compressive stresses. The specimens were however still fatigued to failure. This enabled the analysis of the effect of the peening induced surface roughness to be analysed. It was found that the shot peened and laser shock peened surface roughness values were significantly higher than the roughness values of the T6 specimens owing to the increased ductility and thus workability of the test specimens. These increased surface roughnesses resulted in the shot peened test specimens failing before the laser shock peened specimens. Both sets of peened specimens failed before the "as machined" and polished test specimens highlighting the role that their induced surface roughnesses had on their fatigue lives. The cross-sectional microstructures of the peened samples in each material condition showed varied changes in the microstructure of the treated aluminium alloy. There was evidence of a large degree of plastic deformation near the surface of shot peened specimens in both material conditions. However, there was limited evidence of changes to the grains structure of the laser shock peened specimens, in both material conditions. In addition, the ability of the laser shock peening process to recover fatigue life in damaged components was also investigated. This brought into question whether the laser shock peening process can be used on a partially fatigued component at the point of crack initiation, in an attempt to further improve the fatigue life of the component. It was found that the laser shock peening of the cracks initiated in fatigue life recovery process did little to effectively recover fatigue life in the damaged components. A degree of life extension was present as cracks re-initiated after a few thousand cycles and was attributed to crack tip closure. This closure led to a general reduction in the fatigue crack growth rate when compared to laser shock peened/polished test specimens fatigued at the same stress.

Al-Si-Mg casting alloys are being used in automotive applications, aerospace applications and other applications requiring heat-treatable permanent mould castings that combine good weldability with high strength and toughness (ASM). These casting alloys are also known for their excellent castability, corrosion resistance and, in particular, .a range of mechanical properties in the heattreated condition. A357 aluminum alloy has been extensively used for semi-solid processing for more than three decades, and a large amount of components like fuel rails, engine mounts, engine brackets and suspension parts have been produced. This alloy is also included in the Statement for Work between the Council for Scientific and Industrial Research (CSIR) and Boeing Co, USA. F357, a hypo-eutectic aluminium alloy, Al-7%Si-0.6%Mg without beryllium, was processed with CSIR-Rheo technology to the Semi-Solid Metal (SSM) state and cast in plates with a 50 Ton High Pressure Die Casting machine. The castings were either left in the as-cast (F) condition or subjected to T4, T4+ or T6 heat treatments prior to laser welding. Welding of aluminium alloys poses many problems like porosity, loss of alloying elements, poor bead geometry and softening of the heat affected zone. Laser welding is however widely used in industrial production owing to the advantages such as low heat input, high welding speed and high production rate. Due to these unique advantages, the potential of autogenous Nd: Y AG laser welding as manufacturing process for this cast aluminium alloy was evaluated. A welding operating window was established and the optimum parameters were found to be a laser power of 3.8 kW at the workpiece and a welding speed of 4 m/min with a twin spot laser light configuration. These laser welding parameters were applied for the welding of the heat treated plates and resulted in very low weld joint porosity and almost no loss of alloying elements. The mechanical properties of age-hardenable Al-Si-Mg alloys are dependent on the rate at which the alloy is cooled after the solution heat treatment Because of the high cooling rate during laser welding, the possibility of producing weld seams through deep penetration laser welding, with mechanical properties matching those of the T6 temper condition, but without a post-weld solid solution heat treatment, was investigated. The quench rate after laser welding was measured and compared well with that measured after solution treatment. The resulting mechanical properties of F357 aluminium welded in the T4 condition and only artificially aged after welding (T4+ condition), compares very well with the T6 base material properties. The strengthening mechanisms obtained during laser welding and the different heat treatments were studied by means of transmission electron microscopy (TEM) and are consistent with the expected precipitation hardening processes in Al-Si-Mg alloys. The quench sensitivity of SSM F357 aluminium alloy is thus sufficiently low to obtain such an increase in strength values during laser welding, that no postweld solution heat treatment is necessary to achieve mechanical properties to the T6 performance specification.

Stress corrosion cracking is one of the leading damage mechanisms in low-pressure turbines in the power generation industry; in LP turbine blades it primarily occurs in the last stage blades. The research investigated the influence of tempering temperature on the microstructure, mechanical properties, and stress corrosion cracking properties of 12% chromium FV566 stainless steel, which is used to manufacture LP turbine blades. The standard heat treatment of the steel comprises of austenitising, quenching and double tempering. Austenitising is carried out at 1050°C for one hour - which is sufficiently long to generate a fully austenitic matrix and to dissolve carbon completely. Subsequently, the material is quenched in air. The high level of alloying elements ensures the complete martensitic transformation, with carbon atoms trapped in the matrix and distributed homogeneously. Thereafter, tempering of the material at 580-600°C enhances the ductility and toughness. Tempering replaces the solid solution strengthening of the dissolved carbon with precipitation strengthening by carbides. The final microstructure of the FV566 steel blades is referred to as tempered martensite. van Rooyen showed that for 12% chromium steel tempering at and above 600°C induces passivity of the material against SCC, while tempering of 12% chromium steels at 450-550°C causes sensitisation of the material and the material exhibits intergranular SCC. From such studies, the motivation arises to investigate the impact of heat-treatment parameters - specifically the impact of tempering temperature on the stress corrosion behaviour of the material. The testing methodology comprises heat treatment of FV566 samples at 1050°C for 1 hour, at 350°C for 1 hour, and thereafter tempering for 1 hour at various tempering temperatures. Each stage of heat treatment is followed by air cooling - followed by analysis of the microstructure, mechanical testing and stress corrosion cracking testing of the specimens at the different temper conditions. Stress corrosion testing was divided into two categories. The first set of tests was carried out with U-bend specimens to determine the susceptibility of materials at different heat treatments to SCC, the time taken for SCC to initiate, and the mode of cracking. The second set of tests was conducted to determine the threshold stress intensity, as a function of crack growth rate, for each heat treatment. The SCC failure mechanism observed was intergranular SCC (IGSCC) by anodic dissolution for the 550°C, 560°C, 570°C, 580°C, 590°C, 600°C and 620°C specimens. The material's resistance to SCC improved with increasing tempering temperature. Specimens tempered at 480°C and 550°C were most susceptible to SCC, while specimens tempered at 600°C The material's resistance to SCC improved with increasing tempering temperature. Specimens tempered at 480°C and 550°C were most susceptible to SCC, while specimens tempered at 600°C were immune to SCC in a 4000-hour period. A change in tempering temperature results in a change in the quantity and type of precipitates formed which results in changes in SCC properties of FV566.

Life assessment of critical components and piping is performed in the electrical power plants in order to prevent structural/component failure and prolong safe operation of the equipment. In the event that these components fail, the consequences can be very costly since this may result in power supply disruptions, component replacements, environmental damages and the loss of human life. Regulations, standards and codes are designed to ensure the safe operation of the power plants. However, on their own, they are not adequate to account for aging power plants that have been in service for more than half of their originally designed lifespans, since failures have been experienced due to in-service aging mechanisms (i.e. temper embrittlement, creep, etc.) and poor engineering and maintenance practises. Mechanical, metallurgical and non-destructive techniques are used to evaluate the condition of the in-service materials in order to aid in these life assessments. The structural integrity assessments utilise material toughness properties as determined through fracture toughness testing, which requires a significant quantity of material, and is therefore cumbersome and expensive. Consequently, several other material property testing techniques are used to aid in structural integrity assessments, such as impact energy, tensile and hardness testing. Through empirical correlations, these test results are used to estimate fracture toughness properties and, consequently, the error bands are expected to be as high as 50%. Due to its small size, the small punch test (SPT) technique can be regarded as a quasi-non-destructive test, and is therefore a preferred method for determining the fracture toughness in aid of structural assessment. The SPT technique involves a compression load from the punch to a sample (ϕ8mm x 0.5mm thick) clamped between clamping and receiving dies. This study aims to develop a test rig that will be used to perform the SPT in order to quantify the level of embrittlement on the ex-service, low-pressure steam turbine material (NiCrMoV steel). The data results acquired from the SPT technique are the reaction load of the punch and the deformed displacement of the sample performed at a constant displacement rate according to CWA 15627:2007. Two SPT rigs were designed, manufactured and commissioned. These two were commissioned using FEM and tensile test results for validations. The steel was subjected to three different conditions: as received (AR), de-embrittled (DE) and hardened (HD). The three types of steel illustrated that the SPT can quantify embrittlement levels through the correlation of tensile, Charpy impact energy and fracture toughness testing.

Includes bibliographical references (leaves 121-125). / The Pt₈V ordering transformation in Pt 11 qt.% V alloys has been studied. The study included determining the thermodynamic stability of Pt₈V, the kinetics of Pt₈V ordering transformation and the strengthening due to the presence of the ordered phase. Transmission electron microscopy, using election diffraction and dark and bright field imaging, and X-ray diffraction were used for structural characterisation. Electrical resistivty was used to investigate the kinetics of Pt₈V ordered phase. Microhardness measurements were used to investigate the Pt₈V ordered phase and its effects on hardness.

Includes bibliographical references. / A study has been conducted on both the particle and slurry erosive wear behaviour of WC-Co hard metal coatings. The coating compositions were WC-12%Co and WC-10%Co-4%Cr and were produced using both the TAFA JP5000 and the METCO Diamond Jet (DJ) thermal spray systems.

Includes bibliographical references (leaves 210-219) / An investigation into high strain rate behaviour of polymer composites was performed by developing a finite element model for a fibre reinforced polymer (FRP) plates impacted at varying strain rates. The work was divided into three facets, firstly to characterize the FRP material at varying strain rates, to develop a constitutive model to elucidate the relationship between strain rate and ultimate stress and lastly to use the experimental data to develop a finite element model. Experimental work performed in support of this model includes material characterization of unidirectional carbon and glass fibre reinforced epoxy at varying impact strain rates. The data is then used to develop a suite of constitutive equations that relate the strain rate, ultimate stress and material loading type. The model is of a linear and non-linear viscoelastic type, depending on the type of loading and is applicable to a FRP plate undergoing out-of-plane stresses. This model incorporates techniques for approximating the quasi-static and dynamic response to general time-varying loads. The model also accounts for the effects of damage, the linear and non-linear viscoelastic constitutive laws reporting failure by instantaneously reducing the relevant elastic modulus to zero. An explicit solver is therefore utilised in order to ensure stability of the numerical procedure. Glass fibre reinforced plastics (GFRP) was found to be more strain rate sensitive in all directions when compared to carbon fibre reinforced plastics (CFRP). The validation process therefore involves plate impact experimental testing on GFRP plates. The data from these experiments compare to within 8% of the finite element model that incorporates both damage and the developed strain rate sensitivity constitutive equations. For the first time a model that includes progressive damage with built-in strain rate sensitivity is developed for these particular FRP systems. Furthermore, the ultimate stress has been related to strain rate using an empirical technique. This technique allows for the prediction of dynamic ultimate stresses given the quasi-static ultimate stresses, again for this particular material systems.

The ultimate goal of this project was to explore alternative and various synthetic routes for the design and fabrication of V@Pt core-shell and bimetallic nanoparticles.

Includes bibliographical references (leaves 110-111). / The focus of this study was the use of powder metallurgy to produce low cost titanium with comparative mechanical properties to wrought titanium. The objectives of this investigation was to produce sintered titanium compacts that represented metal made by the Direct Powder Rolling method. The critical strain (ɛC) required to induce recrystallization following deformation was determined by hot compressing wrought titanium samples. Finally sintered titanium samples were hot compressed at ɛC and the changes to the microstructure, porosity and mechanical properties was assessed.