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Stainless steel 316 was examined for compatibility with the eutectic mixtures of NaCl + Na2CO3 and NaCl + Na2SO4 at 700 °C and Li2CO3 + K2CO3 + Na2CO3 at 450 °C in air for thermal energy storage. Electrochemical measurements combined with advanced microscopy and microanalysis techniques were employed. NaCl + Na2CO3 was found as the most aggressive salt at 700 °C. The attack morphology on the surface was uniform corrosion with no localized degradation at 450 °C. Microscopy observations showed grain boundary oxidative attack as the primary corrosion mechanism at 700 °C with depletion of alloying elements from grain boundaries.

The study was conducted using equipment of the Center of X-ray Diffraction Studies and the Center for Microscopy and Microanalysis of the Research Park at Saint Petersburg State University, as well as the analytical laboratory of OJSC MMC Norilsk Nickel in Saint Petersburg.

Degradation of an Inconel 601 superalloy subjected to a eutectic mixture of carbonate salt at 450 °C was studied using advanced microscopy and microanalysis techniques. On the outside of the vessel, long term exposure to elevated temperature led to intergranular stress corrosion cracking via a stress assisted oxidation process. Elemental analysis verified diffusion controlled de-alloying of Ni and Cr from grain boundaries. Transmission electron microscopy showed that a (CrFeNiAl)3O4 oxide phase was formed at grain boundaries as a result of oxygen penetration. Intergranular cracking appeared due to the presence of residual stresses and microstructural heterogeneities facilitated the crack branching.

Particulate reinforced Al alloy composites (AlMCs) are recognized as important structural materials due to their lightweight, high modulus and strength and high wear resistance. In order to understand the effect of matrix, reinforcement and secondary processing techniques on the microstructure development and mechanical properties of AlMCs produced by powder metallurgy routes, Al alloy composites reinforced with three types of reinforcements by different secondary processing techniques have been produced and examined. Fabrication of Al or 6061Al alloy based composites reinforced with nano-sized SiC particles (~500nm), micro-sized ( After cold rolling, the evolution in microstructure, texture and strength has been analysed. A typical near β fibre texture with highest intensities near Copper and Brass orientations has been developed for 6061Al/NQX and 6061Al/Nb composites. For 6061Al/SiC composites, a randomized texture with very small grains has achieved due to the presence of the non-deformable SiC particles. Mechanical property tests including microhardness, three-point bending tests and tensile tests have been carried out on cold rolled samples and the results exhibit some level of improvement when compared with as-extruded samples due to work hardening. Finally, the work moves on to the general discussion based on the previous result chapters. The microstructural development related to reinforcement, matrix and interfacial areas during extrusion and cold rolling has been summarised and the correlation between microstructure and mechanical properties has been discussed. The thesis provides a thorough understanding of AlMCs produced by powder metallurgy routes in terms of matrix, reinforcement and processing techniques. It can provide reference to the future development of AlMCs for high strength applications.

Hardness measurements and Three-Dimensional Atom Probe (3DAP) were used to characterize the early stages of precipitation in three different Al-Mg-Si alloys (Al-0.50 wt%Mg-1.00 wt%Si) with different Cu contents (0.03 wt%, 0.15 wt%, or 0.80 wt% Cu). Heat treatments were chosen to simulate an industrial production line for car body-sheet material and included natural ageing (NA), pre-ageing at 80 °C (PA), paint-bake ageing at 180 °C (PB) and 10 second ageing at 180 °C (spike). The Cu content and the chosen heat treatments were found to influence the microstructural evolution of the alloy considerably. Based on the determined microstructures and matrix solute concentrations, mechanisms for the effect of NA, PA and Cu additions were proposed. NA had a deleterious effect on the PB hardening response, which was delayed dramatically after 20 minutes NA or longer. When the NA time was 1 minute, β" precipitates were formed within 30 minutes PB resulting in high hardness of the alloy. The delay with NA time was caused by a decrease in the nucleation rate of elongated precipitates during the subsequent PB. This decrease was thought to be due to a combination of a decrease in the matrix solute concentrations and clusters acting as vacancy sinks. PA before NA improved the PB response due to the formation of a high density of short elongated precipitates. Small Mg-Si clusters were detected after both NA and PA. Clusters formed during PA were found to be, on average, Mg-richer and larger than those formed during NA. Larger clusters were found to be more stable during PB and, upon PB, to grow into nucleation sites for elongated precipitates. Application of a spike before PA resulted in faster growth of clusters during PA. Growth of clusters and nucleation of short elongated precipitates during PB was found to be enhanced with increasing Cu content when no PA was given. Cu was found to be present in all precipitates and clusters in the alloy with the highest Cu content. These precipitates were thought to be precursors to the Q' phase.

This thesis describes the design, manufacture and characterisation of thick vacuum plasma sprayed tungsten (W) coatings on steel substrates. Fusion is a potentially clean, sustainable, energy source in which nuclear energy is generated via the release of internal energy from nuclei. In order to fuse nuclei the Coulomb barrier must be breached - requiring extreme temperatures or pressures – akin to creating a ‘star in a box’. Tungsten is a promising candidate material for future fusion reactors due to a high sputtering threshold and melting temperature. However, the large coefficient of thermal expansion mismatch with reactor structural steels such as the low activation steel Eurofer’97 is a major manufacturing and in-service problem. A vacuum plasma spraying approach for the manufacture of tungsten and tungsten/steel graded coatings has been developed successfully. The use of graded coatings and highly textured 3D interface surfi-sculpt substrates has been investigated to allow the deposition of thick plasma sprayed tungsten coatings on steel substrates. Finite element models have been developed to understand the residual stresses that develop in W/steel systems and made use of experimental measurements of coating thermal history during manufacture and elastic moduli measured by nano-indentation. For both the graded and surfi-sculpt coating, the models have been used to understand the mechanism of residual stress redistribution and relief in comparison with simple W on steel coatings, particularly by consideration of stored strain energy. In the case of surfi-sculpt W coatings, the patterned substrate gave rise to regular stress concentrating features, and allowed 2mm thick W coatings to be produced reproducibly without delamination. Preliminary through thickness residual stress measurements were compared to model predictions and provided tentative evidence of significant W coating stress relief by regulated coating segmentation.

Reduced activation oxide dispersion strengthened (ODS) steels are candidate alloys for use in fusion reactor systems and are fabricated by mechanically alloying yttrium oxide to a reduced activation ferritic steel powder. The product is consolidated at high temperature by hot isostatic pressing (HIP), producing a dispersion of nanometre sized oxide particles throughout the ferritic microstructure. These particles have been shown to both improve the high temperature mechanical properties of the alloy and provide trapping sites for helium gas. The use of these particles to sequester helium is of particular significance in the development of a structural ODS steel for fusion reactor systems. A fusion power reactor, based on the ITER design, is expected to produce over 2000 appm transmutant helium in any steel components exposed to the core neutron flux. At these gas concentrations, conventional steels undergo severe swelling and embrittlement, motivating the development of materials capable of managing helium accumulation. This thesis investigates the use of the oxide particle dispersion in sequestering helium introduced by ion implantation. An initial characterisation of a model Fe-14Cr-0.25Y2O3 (wt%) system was completed using high resolution transmission electron microscopy (HRTEM) and atom probe tomography (APT). This demonstrated the efficacy of the production methods and the gas trapping capabilities of the oxide particles via argon gas, introduced during the mechanical alloying process. The subsequent consolidation of a full set of Fe-14Cr-3W-0.2Ti-0.25Y2O3 (wt%) ODS alloys at 1150°C, 1050 °C and 950 °C produced a systematic variation in the density of the particle dispersion. The characterisation of these materials using APT provided an insight into the consistent Y2Ti3O5 particle chemistry found in each consolidation, and identified a stoichiometric shift from Y2Ti3O5 to YTiO2 following short term annealing periods at 1000°C. Though further work is required, this shift is thought to be consistent with a thermodynamically mediated transition of the metastable clusters to stable oxide particles. Following implantation with 2000 appm helium and examination under TEM, the helium bubble and particle densities were found to be closely correlated thus providing evidence for an association between the particles and the gas bubbles. Controlling the helium bubble density via the particle dispersion demonstrates the potential use of processing temperature in controlling how helium accumulates in an implanted ODS microstructure. The effects of both bubble and particle densities on mechanical properties were investigated further using nanoindentation methods. Significant local variation in the hardness of the ODS steels was found to result from the bimodal grain size distribution of the material. By using only those measurements taken from large grained regions of the ODS, the grain refinement and particle hardening effects could be deconvolved and used to quantify particle hardening using a dispersed barrier model. The significant hardening effects with helium addition observed in the reference alloys were found to be almost entirely absent from the ODS systems, though anomalous softening in the 950°C consolidation indicated a potentially unexpected interaction between the bubble and particle populations. A possible explanation for this anomaly and a proposal for further work to establish its origin is discussed.

The factors controlling the reliability of Pb-free solders when subject to thermomechanical regimes relevant to the harsh aerospace environment have been studied. Ball grid array (BGAs) typical of microelectronic devices have been manufactured in-house and subjected to isothermal ageing and thermal cycling. The BGAs comprised both Cu and Ni-Au metallizations, Pb-free Sn-Ag-Cu 400 and 600μm solder balls, FR4 and Al2O3 boards, and included circuits to measure resistance changes due to damage in the joints during thermal cycling. Microstructural evolution within the solders balls and complex interfacial reactions were studied in all configurations using various types of electron microscopy. The mechanical properties of the different phases formed within solder joints were studied using nanoindentation at room and elevated temperatures up to 175°C for the first time. Intermetallic compounds (IMCs) were stiff, hard and brittle with very low creep rates, while the softer primary Sn, eutectic regions and Cu metallization readily underwent creep. Two-dimensional finite element analysis (FEA) of nanoindentation was used to understand better the physical meaning of nanoindentation creep data. Reliability experiments comprised both thermal cycling and FEA of BGAs. The difference in coefficient of thermal expansion (CTE) in the BGA materials caused interfacial fatigue damage in the solder joints, which was detected primarily at the solder/metallization interface of the outermost, most strained solder joint. Accumulated creep strain per cycle at this interface was evaluated using 3D FEA of the stress-strain state of the BGA and results calibrated against experimental BGA mean lifetimes using the Coffin-Mason relationship. Nanoindentation combined with FEA has been shown to be a viable route for the rapid assessment of creep performance and lifetime in lead-free solders under aerospace thermal cycles.

The combination of X-ray imaging and diffraction techniques provides a unique tool for structural and mechanical analysis of engineering components. A variety of modes can be employed in terms of the spatial resolution (length-scale), time resolution (frequency), and the nature of the physical quantity being interrogated. This thesis describes my contributions towards the development of novel X-ray “rich” imaging experimental techniques and data interpretation. The experimental findings have been validated via comparison with other experimental methods and numerical modelling. The combination of fast acquisition rate and high penetration properties of X-ray beams allows the collection of high-resolution 3-D tomographic data sets at submicron resolution during in situ deformation experiments. Digital Volume Correlation analysis tools developed in this study help understand crack propagation mechanisms in quasi-brittle materials and elasto-plastic deformation in co-sprayed composites. For the cases of crystalline specimens where the knowledge of “live” or residual elastic strain distributions is required, diffraction techniques have been advanced. Diffraction Strain Tomography (DST) allows non-destructive reconstruction of the 2-D (in-plane) variation of the out-of-plane strain component. Another diffraction modality dubbed Laue Orientation Tomography (LOT), a grain mapping approach has been proposed and developed based on the translate-rotate tomographic acquisition strategy. It allows the reconstruction of grain shape and orientation within polycrystalline samples, and provides information about intragranular lattice strain and distortion. The implications of this method have been thoroughly investigated. State-of-the-art engineering characterisation techniques evolve towards scrutinising submicron scale structural features and strain variation using the complementarity of X-ray imaging and diffraction. The first successful feasibility study is reported of in operando stress analysis in an internal combustion engine. Finally, further advancement of ‘rich’ imaging techniques is illustrated via the first successful application of Time-of-Flight Neutron Diffraction Strain (TOF-NDST) tomography for non-destructive reconstruction of the complete strain tensor using an inverse eigenstrain formulation.

Reduced-activation ferritic steels are considered as the primary candidate materials for structural applications within nuclear fusion power plants. It is known that by mechanically alloying ferritic steel powder with Y (usually in the form of Y₂O₃) then consolidating the material by hot isostatic pressing, a nanoscale dispersion of oxygen rich nanoclusters as small as ~2nm is introduced into the microstructure. This vastly improves high temperature strength and creep resistance, and the nanoclusters also act as trapping sites for helium and point defects produced under irradiation.In this thesis, the evolution of the oxide nanoclusters in a Fe-14Cr-2W-0.3Ti & 0.3Y₂O₃ ODS alloy was investigated primarily using atom probe tomography. The microstructure was characterised at various points during processing to give an insight into the factors influencing the formation of the nanoclusters. It was found that the nanoclusters nucleated during the mechanical alloying stage, then followed near classical nucleation and growth mechanisms keeping the same composition of ~8%Y, ~12%Ti,~25%O and ~45%Cr throughout. The formation and evolution of 5-15nm grain boundary oxides was also observed, and these were shown to form first as Cr₂O₃ particles that subsequently transform into a Y-Ti-O based oxide on further processing.The influence of mechanical alloying with 0.5wt.%Fe₂Y rather than 0.3wt.%Y₂O₃ was also investigated, and this showed that there was no difference in the final microstructure produced provided the level of Ti in the starting powder was tightly controlled. Without sufficient Ti, the nanoclusters were Y-O based and ~6nm diameter. Both the Y-O and Y-Ti-O nanoclusters were moderately stable on annealing at 1200°C for up to 100 hours, with only minimal coarsening observed. Ti was found not to influence the coarsening rate of the nanoclusters significantly.The stability of the oxide nanoclusters under irradiation was investigated by using Fe²⁺ ion irradiation to simulate displacement cascade damage in the ODS-Eurofer material (the official European candidate material for testing in the ITER fusion test reactor). Doses up to ~6 dpa at 400°C were used, and there was no significant change to the nanocluster distribution. However segregation of Mn to dislocations was observed after irradiation.These results indicate that ODS steels are good candidate structural materials, as the microstructure is stable at high temperature and under irradiation. The starting powders, and processing parameters need to be tightly controlled in order to produce the optimal material for use in service.

Austenitic stainless steels are frequently used in the cooling circuits of nuclear reactors. It has been found that cold-worked 304 stainless steels can be particularly susceptible to stress corrosion cracking at the operating conditions of such reactors. Despite more than 130 years of research underlying mechanisms are still not properly understood. For this reason, the effects of cold-work and applied stress on the oxidation behaviour of 304SS have been studied in this thesis.A set of samples with/without prior cold-work, and with/without stress applied during oxidation, were oxidized in autoclaves under simulated pressurised water reactor primary circuit conditions. Atom-probe tomography and analytical transmission electron microscopy were used to investigate the local chemistry and microstructure in the different samples tested. Regions containing grain boundaries, deformation bands, and matrix material in contact with the environment, were extracted from the coupon specimens with a focused ion beam machine. Cross-sections of crack tips were studied with secondary ion mass spectrometry and electron backscatter diffraction. The compositions of oxides grown along the surface and the different microstructural features were analysed. Fe-rich spinels were found at the surface and Cr-rich spinels were observed along fast diffusion paths. Ni-enrichment was found at the metal/oxide interfaces and a Ni-rich phase was detected in precipitates ahead of grain boundary oxides. Li was observed in all oxidised regions and B segregation, originating from impurities in the alloy, was observed in grain boundaries and crack tip oxides. Cavities and hydrogen associated with Ni-rich regions were found ahead of the bulk Cr-rich oxide in some of the samples.The implications of these findings for the understanding of SCC mechanisms are discussed. It is suggested that Ni precipitation as well as the presence of deformation bands may play an important role in controlling SCC susceptibility in 304 stainless steel. A modification of the film-rupture model including internal oxidation and fast diffusion along H-stabilised vacancies in strain fields at the crack front is proposed.

Ferritic ODS steels show improved high temperature strength and irradiation tolerance compared with conventional ferritic steels, and are one of the key potential materials for fusion blanket structural applications. The processing of ODS steels is critical to their subsequent performance; however knowledge of the optimum processing approaches for these alloys is not complete. The microstructural evolution of ODS steels containing Y2O3 and other additions during manufacture has been investigated and the processing conditions optimised based on microstructural and mechanical investigations. Ferritic powders with Y2O3 and other additions were investigated, primarily using analysis on the micro- and nano-scale, with an emphasis on identifying the requirements for homogenization of the Y within the steel matrix. The Y2O3 dispersion and subsequent development of the nano-precipitates during thermal treatment was investigated using in-situ neutron diffraction. The nano-precipitates were resolved at approximately 900◦C after 1hr, with coarsening and/or re-precipitation progressively increasing at higher temperatures. A significantly increased number density of nano-precipitates (∼2x1023m−3 to ∼7x1023m−3) was established by hot isostatically pressing an Fe-14Cr-3W-0.2Ti0.25Y2O3 alloy at 950◦C compared with more traditional temperatures at 1150◦C, attributed to the increased coarsening and/or re-precipitation of the nano-precipitates at the higher temperatures. The influence of the mechanical alloy (MA)ing conditions on bulk mechanical properties was investigated using four point bend. The highest fracture toughness of ∼55MN/m3/2 and ultimate strength of ∼1450MPa was achieved under conditions that minimised the mechanical alloying time and increased the average final size of the powders. An Fe-14Cr-3W-0.2Ti-0.25Y2O3 (wt%) ODS alloy manufactured under optimised conditions showed a bi-modal grain structure size distribution and had a comparatively high yield strength of >1200MPa at 20◦C and >330MPa at 700◦C. The grain structure and high yield strength were attributed to the random distribution of 25nm radius of gyration (Rg) Y, Ti and O rich nano-precipitates randomly dispersed throughout the alloy. Long term thermal ageing (750hr at 1000◦C) reduced the room temperature yield strength and increased the proportion of larger grains in the bi-modal distribution, but high temperature yield strength was remarkably stable.

The addition of small amounts of boron to 9 to 12 pct chromium steels has been found to decrease their creep rate at 823 K to 923 K (550 °C to 650 °C). In this article, the behavior of boron during austenitizing, tempering, and isothermal heat treatment at 873 K (600 °C) is studied using high-resolution microscopy and microanalysis as well as using atomistic modeling. It was found that increasing the boron content from 9 to 40 ppm decreased the coarsening constant of M23C6 by a factor of almost 2. Most of the added boron was incorporated in M23C6. Atomistic modeling showed that boron diffusion in ferrite is dominated by an interstitial mechanism at 873 K (600 °C). However, the generation of vacancies when carbide precipitates dissolve may promote a distribution with substitutional boron atoms. The absence of a fast mechanism for the transition from substitutional to interstitial occupancy will make the slow substitutional boron diffusion in the matrix rate controlling for the coarsening process.

Nickel laterites are considerable sources of nickel. To be successfully exploited it is important to know the mineralogical and microstructural characteristics of the ore. Besides, the identification of the mineralogical components as well as the fabric description, can lead to the interpretation of the mechanism of deposit genesis. The aim of the present study is the microscopic and microanalytical investigation of the Fe-Ni ores from Komnina Vermion area (N.W. Greece). The mineralogical composition of the ore is mainly hematite, quartz, chromite and chlorite, while in minor quantities goethite, nickeliferous chlorite, serpentine, talc and calcite are also present. The ore structure is allotriomorphic inequigranular and the texture is oolitic-pisolitic. According to microscopic examination the deposit can be registered as a secondary pseudo-autochthonous.

Laser cladding of stainless steel substrate was carried out using Ni-32Mo-15Cr-3Si (wt%) alloy powder. Laser cladding parameters were optimized to obtain defectfree and metallurgically bonded clad. Variation in solidification rate, cooling rate and compositional variation resulted in heterogeneous microstructure. Microstructure was found to be distinctly different in regions of clad cross-section. Majority of the region was found to consist of eutectic of Mo-rich hcp intermetallic Laves phase and NiFe fcc gamma solid solution phases. Extensive microstructural examinations of different clad regions have been carried out using microscopy and microanalysis techniques.

We studied the changes in the structure and carbide particle size in 1.25Cr–1Mo–0.25V steel under 600 °C and 168 MPa, after 4000 h service. We used microscopy and microanalysis techniques to analyze the carbide particles. We performed a complementary theoretical study on the chemical bonding and electronic structure of the carbide–Fe matrix interaction. The results contribute to the understanding of the changes in the alloy microstructure caused by the carburization phenomenon.

Precision thick chip resistors are used in a variety of different industries, from telecommunications to automotive electronics, and as such can be exposed to mild and aggressive corrosive environments. This paper investigates the corrosion performance of two generic precision thick chip resistors in a controlled corrosive atmosphere consisting of 60degC, 4 ppm H2S and water vapor in purified air. The resistors were exposed in an environmental chamber for periods of 5, 10, 15, 30, and 60 days. Following exposure, the samples were cross sectioned and subjected to surface analysis using microscopy and microanalysis. After the initial stages of exposure, corrosion was observed on only one of the two types of resistors. The corrosion developed because H2S gas and water vapor diffuses through the thin protective organic layer on the resistor, and subsequently reacts with the silver conductor layer. Corrosion was facilitated by poor overlapping of the solder and nickel layer and, in particular the glass binder over the glass overcoat, which allowed silver and sulphur to diffuse along the interface. In addition, this poor overlapping allowed contact between the nickel layer and the silver layer resulting in the development of an electrochemical corrosion cell. The main corrosion products that developed were silver sulfide (Ag2S) and nickel sulphur residue.

The combination of X-ray imaging and diffraction techniques provides a unique tool for structural and mechanical analysis of engineering components. A variety of modes can be employed in terms of the spatial resolution (length-scale), time resolution (frequency), and the nature of the physical quantity being interrogated. This thesis describes my contributions towards the development of novel X-ray “rich” imaging experimental techniques and data interpretation. The experimental findings have been validated via comparison with other experimental methods and numerical modelling. The combination of fast acquisition rate and high penetration properties of X-ray beams allows the collection of high-resolution 3-D tomographic data sets at submicron resolution during in situ deformation experiments. Digital Volume Correlation analysis tools developed in this study help understand crack propagation mechanisms in quasi-brittle materials and elasto-plastic deformation in co-sprayed composites. For the cases of crystalline specimens where the knowledge of “live” or residual elastic strain distributions is required, diffraction techniques have been advanced. Diffraction Strain Tomography (DST) allows non-destructive reconstruction of the 2-D (in-plane) variation of the out-of-plane strain component. Another diffraction modality dubbed Laue Orientation Tomography (LOT), a grain mapping approach has been proposed and developed based on the translate-rotate tomographic acquisition strategy. It allows the reconstruction of grain shape and orientation within polycrystalline samples, and provides information about intragranular lattice strain and distortion. The implications of this method have been thoroughly investigated. State-of-the-art engineering characterisation techniques evolve towards scrutinising submicron scale structural features and strain variation using the complementarity of X-ray imaging and diffraction. The first successful feasibility study is reported of in operando stress analysis in an internal combustion engine. Finally, further advancement of ‘rich’ imaging techniques is illustrated via the first successful application of Time-of-Flight Neutron Diffraction Strain (TOF-NDST) tomography for non-destructive reconstruction of the complete strain tensor using an inverse eigenstrain formulation.

Particulate reinforced Al alloy composites (AlMCs) are recognized as important structural materials due to their lightweight, high modulus and strength and high wear resistance. In order to understand the effect of matrix, reinforcement and secondary processing techniques on the microstructure development and mechanical properties of AlMCs produced by powder metallurgy routes, Al alloy composites reinforced with three types of reinforcements by different secondary processing techniques have been produced and examined. Fabrication of Al or 6061Al alloy based composites reinforced with nano-sized SiC particles (~500nm), micro-sized ( After cold rolling, the evolution in microstructure, texture and strength has been analysed. A typical near β fibre texture with highest intensities near Copper and Brass orientations has been developed for 6061Al/NQX and 6061Al/Nb composites. For 6061Al/SiC composites, a randomized texture with very small grains has achieved due to the presence of the non-deformable SiC particles. Mechanical property tests including microhardness, three-point bending tests and tensile tests have been carried out on cold rolled samples and the results exhibit some level of improvement when compared with as-extruded samples due to work hardening. Finally, the work moves on to the general discussion based on the previous result chapters. The microstructural development related to reinforcement, matrix and interfacial areas during extrusion and cold rolling has been summarised and the correlation between microstructure and mechanical properties has been discussed. The thesis provides a thorough understanding of AlMCs produced by powder metallurgy routes in terms of matrix, reinforcement and processing techniques. It can provide reference to the future development of AlMCs for high strength applications.

Ferritic ODS steels show improved high temperature strength and irradiation tolerance compared with conventional ferritic steels, and are one of the key potential materials for fusion blanket structural applications. The processing of ODS steels is critical to their subsequent performance; however knowledge of the optimum processing approaches for these alloys is not complete. The microstructural evolution of ODS steels containing Y2O3 and other additions during manufacture has been investigated and the processing conditions optimised based on microstructural and mechanical investigations. Ferritic powders with Y2O3 and other additions were investigated, primarily using analysis on the micro- and nano-scale, with an emphasis on identifying the requirements for homogenization of the Y within the steel matrix. The Y2O3 dispersion and subsequent development of the nano-precipitates during thermal treatment was investigated using in-situ neutron diffraction. The nano-precipitates were resolved at approximately 900◦C after 1hr, with coarsening and/or re-precipitation progressively increasing at higher temperatures. A significantly increased number density of nano-precipitates (∼2x1023m−3 to ∼7x1023m−3) was established by hot isostatically pressing an Fe-14Cr-3W-0.2Ti0.25Y2O3 alloy at 950◦C compared with more traditional temperatures at 1150◦C, attributed to the increased coarsening and/or re-precipitation of the nano-precipitates at the higher temperatures. The influence of the mechanical alloy (MA)ing conditions on bulk mechanical properties was investigated using four point bend. The highest fracture toughness of ∼55MN/m3/2 and ultimate strength of ∼1450MPa was achieved under conditions that minimised the mechanical alloying time and increased the average final size of the powders. An Fe-14Cr-3W-0.2Ti-0.25Y2O3 (wt%) ODS alloy manufactured under optimised conditions showed a bi-modal grain structure size distribution and had a comparatively high yield strength of >1200MPa at 20◦C and >330MPa at 700◦C. The grain structure and high yield strength were attributed to the random distribution of 25nm radius of gyration (Rg) Y, Ti and O rich nano-precipitates randomly dispersed throughout the alloy. Long term thermal ageing (750hr at 1000◦C) reduced the room temperature yield strength and increased the proportion of larger grains in the bi-modal distribution, but high temperature yield strength was remarkably stable.

Reduced-activation ferritic steels are considered as the primary candidate materials for structural applications within nuclear fusion power plants. It is known that by mechanically alloying ferritic steel powder with Y (usually in the form of Y₂O₃) then consolidating the material by hot isostatic pressing, a nanoscale dispersion of oxygen rich nanoclusters as small as ~2nm is introduced into the microstructure. This vastly improves high temperature strength and creep resistance, and the nanoclusters also act as trapping sites for helium and point defects produced under irradiation.In this thesis, the evolution of the oxide nanoclusters in a Fe-14Cr-2W-0.3Ti & 0.3Y₂O₃ ODS alloy was investigated primarily using atom probe tomography. The microstructure was characterised at various points during processing to give an insight into the factors influencing the formation of the nanoclusters. It was found that the nanoclusters nucleated during the mechanical alloying stage, then followed near classical nucleation and growth mechanisms keeping the same composition of ~8%Y, ~12%Ti,~25%O and ~45%Cr throughout. The formation and evolution of 5-15nm grain boundary oxides was also observed, and these were shown to form first as Cr₂O₃ particles that subsequently transform into a Y-Ti-O based oxide on further processing.The influence of mechanical alloying with 0.5wt.%Fe₂Y rather than 0.3wt.%Y₂O₃ was also investigated, and this showed that there was no difference in the final microstructure produced provided the level of Ti in the starting powder was tightly controlled. Without sufficient Ti, the nanoclusters were Y-O based and ~6nm diameter. Both the Y-O and Y-Ti-O nanoclusters were moderately stable on annealing at 1200°C for up to 100 hours, with only minimal coarsening observed. Ti was found not to influence the coarsening rate of the nanoclusters significantly.The stability of the oxide nanoclusters under irradiation was investigated by using Fe²⁺ ion irradiation to simulate displacement cascade damage in the ODS-Eurofer material (the official European candidate material for testing in the ITER fusion test reactor). Doses up to ~6 dpa at 400°C were used, and there was no significant change to the nanocluster distribution. However segregation of Mn to dislocations was observed after irradiation.These results indicate that ODS steels are good candidate structural materials, as the microstructure is stable at high temperature and under irradiation. The starting powders, and processing parameters need to be tightly controlled in order to produce the optimal material for use in service.

Austenitic stainless steels are frequently used in the cooling circuits of nuclear reactors. It has been found that cold-worked 304 stainless steels can be particularly susceptible to stress corrosion cracking at the operating conditions of such reactors. Despite more than 130 years of research underlying mechanisms are still not properly understood. For this reason, the effects of cold-work and applied stress on the oxidation behaviour of 304SS have been studied in this thesis.A set of samples with/without prior cold-work, and with/without stress applied during oxidation, were oxidized in autoclaves under simulated pressurised water reactor primary circuit conditions. Atom-probe tomography and analytical transmission electron microscopy were used to investigate the local chemistry and microstructure in the different samples tested. Regions containing grain boundaries, deformation bands, and matrix material in contact with the environment, were extracted from the coupon specimens with a focused ion beam machine. Cross-sections of crack tips were studied with secondary ion mass spectrometry and electron backscatter diffraction. The compositions of oxides grown along the surface and the different microstructural features were analysed. Fe-rich spinels were found at the surface and Cr-rich spinels were observed along fast diffusion paths. Ni-enrichment was found at the metal/oxide interfaces and a Ni-rich phase was detected in precipitates ahead of grain boundary oxides. Li was observed in all oxidised regions and B segregation, originating from impurities in the alloy, was observed in grain boundaries and crack tip oxides. Cavities and hydrogen associated with Ni-rich regions were found ahead of the bulk Cr-rich oxide in some of the samples.The implications of these findings for the understanding of SCC mechanisms are discussed. It is suggested that Ni precipitation as well as the presence of deformation bands may play an important role in controlling SCC susceptibility in 304 stainless steel. A modification of the film-rupture model including internal oxidation and fast diffusion along H-stabilised vacancies in strain fields at the crack front is proposed.

In industrial metal-forming processes, quantitative and physical models are required to control and optimize the microstructure of the finished products. A detailed understanding of the behavior of polycrystalline materials during deformation processes is essential to develop such models. A number of instruments and analytical tools are available for deformation studies within the microscopy and microanalysis community. In a scanning electron microscope (SEM), the visualization and characterization of deformed microstructures are carried out with electron channeling contrast imaging (ECCI) and electron backscattered diffraction (EBSD). These SEM studies provide a nanoscale spatial resolution, a large field of view and statistically reliable information on a bulk specimen [1]. In this study, complex variations of backscattering intensity (IBSE) were observed in ECCI micrographs of magnesium (Mg) grains after the uniaxial hot compression test. The variations of IBSE across the ECCI micrographs were attributed to plastic deformation of the Mg grains [2]. Recovery, recrystallization and phase transformation processes occurred simultaneously during deformation at high temperature. The interactions between the three processes lead to a complex deformed microstructure consisting of dynamically recrystallized grains and precipitates. The deformed microstructure varied with different deformation variables such as temperature, strain rate and strain [3,4].

The factors controlling the reliability of Pb-free solders when subject to thermomechanical regimes relevant to the harsh aerospace environment have been studied. Ball grid array (BGAs) typical of microelectronic devices have been manufactured in-house and subjected to isothermal ageing and thermal cycling. The BGAs comprised both Cu and Ni-Au metallizations, Pb-free Sn-Ag-Cu 400 and 600μm solder balls, FR4 and Al2O3 boards, and included circuits to measure resistance changes due to damage in the joints during thermal cycling. Microstructural evolution within the solders balls and complex interfacial reactions were studied in all configurations using various types of electron microscopy. The mechanical properties of the different phases formed within solder joints were studied using nanoindentation at room and elevated temperatures up to 175°C for the first time. Intermetallic compounds (IMCs) were stiff, hard and brittle with very low creep rates, while the softer primary Sn, eutectic regions and Cu metallization readily underwent creep. Two-dimensional finite element analysis (FEA) of nanoindentation was used to understand better the physical meaning of nanoindentation creep data. Reliability experiments comprised both thermal cycling and FEA of BGAs. The difference in coefficient of thermal expansion (CTE) in the BGA materials caused interfacial fatigue damage in the solder joints, which was detected primarily at the solder/metallization interface of the outermost, most strained solder joint. Accumulated creep strain per cycle at this interface was evaluated using 3D FEA of the stress-strain state of the BGA and results calibrated against experimental BGA mean lifetimes using the Coffin-Mason relationship. Nanoindentation combined with FEA has been shown to be a viable route for the rapid assessment of creep performance and lifetime in lead-free solders under aerospace thermal cycles.

Hardness measurements and Three-Dimensional Atom Probe (3DAP) were used to characterize the early stages of precipitation in three different Al-Mg-Si alloys (Al-0.50 wt%Mg-1.00 wt%Si) with different Cu contents (0.03 wt%, 0.15 wt%, or 0.80 wt% Cu). Heat treatments were chosen to simulate an industrial production line for car body-sheet material and included natural ageing (NA), pre-ageing at 80 °C (PA), paint-bake ageing at 180 °C (PB) and 10 second ageing at 180 °C (spike). The Cu content and the chosen heat treatments were found to influence the microstructural evolution of the alloy considerably. Based on the determined microstructures and matrix solute concentrations, mechanisms for the effect of NA, PA and Cu additions were proposed. NA had a deleterious effect on the PB hardening response, which was delayed dramatically after 20 minutes NA or longer. When the NA time was 1 minute, β" precipitates were formed within 30 minutes PB resulting in high hardness of the alloy. The delay with NA time was caused by a decrease in the nucleation rate of elongated precipitates during the subsequent PB. This decrease was thought to be due to a combination of a decrease in the matrix solute concentrations and clusters acting as vacancy sinks. PA before NA improved the PB response due to the formation of a high density of short elongated precipitates. Small Mg-Si clusters were detected after both NA and PA. Clusters formed during PA were found to be, on average, Mg-richer and larger than those formed during NA. Larger clusters were found to be more stable during PB and, upon PB, to grow into nucleation sites for elongated precipitates. Application of a spike before PA resulted in faster growth of clusters during PA. Growth of clusters and nucleation of short elongated precipitates during PB was found to be enhanced with increasing Cu content when no PA was given. Cu was found to be present in all precipitates and clusters in the alloy with the highest Cu content. These precipitates were thought to be precursors to the Q' phase.

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010.

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010.

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010.

Extended abstract of a paper presented at the Pre-Meeting Congress: Materials Research in an Aberration-Free Environment, at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, July 31 and August 1, 2004.

Plutonium (Pu), with an atomic number of 94, is the highest atomic number naturally occurring element on Earth. It is formed when naturally occurring Uranium 238 captures a neutron that can be created by spontaneous fission and alphaneutron reactions. The natural abundance of terrestrial Pu is very small; its concentration is about one part in 10 of the uranium present in naturally occurring uranium ores. The first man-made plutonium was produced at the University of California cyclotron and identified on February 23, 1941. Just a few months after the first Pu was produced it became clear how metallurgically complex this material is. Plutonium is known to have six allotropes (crystalline forms) at atmospheric pressure, between room temperature and 640°C, the melting point of the pure metal. This is the largest number of allotropes known for any element.

Focused Ion Beam (FIB) specimen preparation for both scanning and transmission electron microscopy (SEM and TEM respectively) has seen an increase in usage over the past few years. The advantage to the FIB is that site specific cross sections (or plan view sections) may be fabricated quickly and reproducibly from numerous types of materials using a finely focused beam of Ga+ ions [1,2]. It was demonstrated by Prenitzer et al. that TEM specimens may be acquired from individual Zn powder particles by employing the FIB LO specimen preparation technique [3]. In this paper, we use the FIB LO technique to prepare TEM specimens from Mount Saint Helens volcanic ash.Volcanic ash from Mount Saint Helens was obtained at the Microscopy and Microanalysis 1998 meeting in Atlanta. TEM analysis of the ash was performed using the FIB lift out technique [1]. Ash powders were dusted onto an SEM sample stud that had been coated with silver paint.

Pure copper samples were exposed in an environmental chamber for 2, 4, 7, 15, and 30 days at 90% relative humidity, 40°C, and 4 ppm hydrogen sulfide (H 2 S). Samples were subsequently subjected to microscopy and microanalysis using different techniques: scanning electron microscopy, energy analysis dispersive X-ray spectroscopy, X-ray diffraction, focused ion beam (FIB), and secondary ion mass spectroscopy. The corrosion samples were cross sectioned and the different corrosion layers were imaged using FIB. After 30 days exposure the predominant corrosion products were copper sulfide (Cu 2 S) and cuprite (Cu 2 O). Once the Cu 2 S reached a minimum thickness, the rate of growth of the layer became parabolic due to the limiting Cu + diffusion through a thickening film. As the layers reach a critical thickness (∼ 1000 nm) internal stresses and defects in the corrosion layer allow virtually free access of H 2 S and O to the underlying layers, consequently accelerating the film growth. ©2007 The Electrochemical Society. [DOI: 10.1149/1.2436612] All rights reserved.

Our understanding of the microstructure and microchemistry of metallic materials has increased dramatically during the last few decades, as modern methods of high resolution microscopy and microanalysis have successively become available. The transmission electron microscope (TEM), the electron microprobe, the scanning electron microscope (SEM) and, more recently, the “analytical electron microscope” (i.e. a scanning transmission electron microscope equipped with an energy dispersive X-ray spectrometer, STEM/EDS) have all produced a wealth of new knowledge and understanding. However, the science of hard metals has probably gained less from these methods than have other branches of metallurgy. This is no doubt due to the difficulty to prepare, from the hard metal materials, the thin foils that are a prerequisite for the study by the high-resolution methods, TEM and STEM/EDS. Electropolishing of materials containing phases as chemically different as refractory carbides and a soft binder phase is very dif f icult1–4, and ion etching is very time consuming5,6.