The structure of molten Au0.81Si0.19, Au0.72Ge0.28 and Ag0.74Ge0.26 alloys with a composition at or near to the eutectic was investigated by using neutron diffraction (ND). The results suggest that the Au-Au distance in the alloys is similar to that of liquid Au, there is a preference for Au-Si bonds and show that there are pre-peaks in the total structure factors for Au0.72Ge0.28 and Ag0.74Ge0.26 at 1.3(2) and 1.6(3) ˚, A−1 respectively. The asymptotic decay of the pair correlation functions was found to agree both with a theoretical prediction based on simple pair potentials and a fractal model for metallic glasses. The structure of glassy (R2O3)0.2(Al2O3)0.2(SiO2)0.6, where R denotes Dy, Ho or a 50:50 mixture of Dy and Ho, was investigated by using the method of isomorphic substitution in ND, x-ray diffraction (XRD) and extended x-ray absorption fine structure (EXAFS) spectroscopy. The network is made from SiO4 tetrahedral units with a distribution of AlO4, AlO5 and AlO6 units giving an average coordination number of 4.5(1). There is a distribution of RO5, RO6, RO7, RO8 and RO9 units with an average coordination number of 7.2(3) and an average R-O distance of 2.33(2) ˚ A. The EXAFS results confirmed that Dy and Ho are isomorphic and were used to refine an RMC model of the structure. R-Al and R-Si nearest neighbour shells with average distances of 3.15(3) and 3.6(1) ˚A were required to fit the EXAFS results. The structure of glassy and liquid ZnCl2 was studied by using ND and XRD. The material has a network structure made from ZnCl4 tetrahedra units which is retained in the liquid at temperatures near to the boiling point. An increase of temperature promotes edge sharing connectivity as inferred from a decrease of the Zn-Zn nearest neighbour distance and average Zn-Cl coordination number. An EXAFS study on crystalline ZnCl2 at room temperature shows that Zn remains 4fold coordinated at pressures less than 1 GPa, is 4+2-fold coordinated at 2-4 GPa, and is 6-fold coordinated above 4 GPa. For liquid ZnCl2, Zn is 4-fold coordinated by Cl at a pressure of about 1 GPa and could be 6-fold coordinated at 2-3 GPa.

No description available.

Stationary shoulder friction stir welding (SSFSW) is a recently developed variant of conventional friction stir welding (FSW). Recent studies have shown that SSFSW can join high strength aluminum alloys with improved mechanical strength and reduced distortion as a result of a narrower and more uniform thermal profile. However, a lack of understanding on the residual stress development in the SSFSW process makes it difficult to assess the structural integrity and delays a widespread application of this technique to industry. This dissertation reports the first systematic investigation into the development of residual stress induced by the SSFSW process and comparison between SSFSW and FSW techniques. Welding residual stresses were experimentally assessed with both the contour method and neutron diffraction. The weld microstructure and hardness distributions were characterized and used to understand the formation of residual stresses during the welding process. The results have shown that for both FSW and SSFSW processes, the residual stresses distribute in the form of ‘M’ shaped profile while the magnitude and size of tensile residual stress zone were effectively reduced (by 25%) in the SSFSW process, even when input welding power was identical. Other improvements seen in the SSFSW process include a reduction in the heat affected zone width, an increase in the minimum hardness and a more uniform through-thickness microstructure and hardness. The dominating welding process parameter affecting the welding residual stress was travel speed as compared to rotation speed and tool downforce. With a 90 degree shaped shoulder, SSFSW has been shown to produce defect-free T-sections by dual fillet welds. For these components, an asymmetrical distribution of microstructure, hardness and residual stresses were found as a consequence of the thermal effects induced by second weld on the first weld. The material softening caused by the first weld provides the potential of utilizing a lower heat input on the subsequent pass so as to optimize the welding parameters.

Residual stresses are the stresses which are present within a component without any external load. They can be introduced through any number of manufacturing processes and in-service conditions, meaning that they are almost ubiquitous in engineering components. The characterisation of residual stress is an important field of research particularly in an engineering context since the effects of residual stress sum with the loads. As a result, the performance of a component can be greatly enhanced, or significantly reduced, by the presence of residual stress depending on the sign of the stress and the applied load. In this EngD thesis the focus has been on the development of residual stress through the manufacturing processes of aero-engine forgings, specifically the turbine disc. The forgings studied were sub-scale geometries of the disc, forged from the nickel-base superalloy RR1000. The overall aim of this work is to improve the understanding of the residual stress generation and relaxation through implementation of advanced experimental characterisation techniques, with a view to improving current stress predicting process modelling capabilities. With this in mind the work has focussed on the use of neutron diffraction and the contour method to characterise residual stress experimentally, while residual stress predictions have been made using finite element modelling. The findings of this research indicated that very large residual stresses were generated as a result of the quenching process, and that these stresses were then relaxed and redistributed by ageing heat treatments and material removal by machining. The results obtained through the two experimental techniques exhibited very strong agreement, indicated a robust experimental process. Comparisons to the finite element predictions highlighted some issues with the current model; in particular it was found that the simulation of quenching could be improved by better definition of the heat transfer at the surface. Furthermore, the level of stress relaxation during ageing was consistently over predicted in the model. This result is thought to be the result of an over-prediction of the level primary creep in the alloy. Subsequent studies will investigate this behaviour further using the newly developed in-situ heat treatment capabilities which have developed as part of this research.

This research investigated the residual stresses in narrow-gap API 5L X65 pipe girth welds in as-welded and after post weld heat treatment (PWHT) conditions. The PWHT included global furnace and local practices. Non-destructive neutron diffraction (ND) strain scanning was carried out on selected pipe spools and strainfree reference samples for the determination of the lattice spacing before and after PWHT. The as-welded and post-heat treatment residual stresses measured in the pipe spools were examined and compared. Experimental work also included full residual stress mapping in the weldment and through-thickness measurement at weld centre and close to the external and internal pipe surfaces. The measured profiles were compared with the recommendations given in British flaw assessment procedure BS 7910 "Guide to methods for assessing the acceptability of flaws in metallic structures" and the UK nuclear industry's R6 procedure. The design, preparation and experimental neutron diffraction measurement procedures for the determination of the strain-free lattice parameter in various configurations of reference samples and in the required directions were discussed. The variability of the lattice spacing in the reference samples was found depended on the specimen manufacture methods and thermal process. Welding residual stresses were also simulated using finite element analysis (FEA) modelling approach. The simulated thermal cycles and transient strains at specific locations were compared with the experimental readings. The residual stress profiles derived from finite element model were compared with the measurements from neutron diffraction. It was found, the measured and simulated, as-welded - residual stress profiles showed good consistency in terms of stress distribution and magnitude to reasonable extent. Measurement results also indicated that local PWHT was effective in reducing the residual stresses in the pipes to a level similar to that achieved by a global approach.

Doctor of Philosophy(PhD) / This project focuses on the examination of the structures of lanthanide containing double perovskites of the type Ba2LnB'O6-d (Ln = lanthanide or Y3+ and B' = Nb5+, Ta5+, Sb5+ and/or Sn4+) using synchrotron X-ray and neutron powder diffraction. The first part of this project examined the relative stability of R3 rhombohedral and I4/m tetragonal structures as the intermediate phase adopted by the series Ba2LnB'O6 (Ln = lanthanide (III) or Y3+ and B' = Nb5+, Ta5+ or Sb5+). It was found that I4/m tetragonal symmetry was favoured when B' was a transition metal with a small number of d electrons, such as Nb5+ or Ta5+. This is due to the presence of p-bonding in these compounds. In the Ba2LnNbO6 and Ba2LnTaO6 series R3 rhombohedral symmetry was, however, favoured over I4/m tetragonal symmetry when Ln = La3+ or Pr3+ due to the larger ionic radius of these cations. The incompatibility of the d0 and d10 B'-site cations in this family of compounds was indicated by significant regions of phase segregation in the two series Ba2Eu1-xPrxNb1-xSbxO6 and Ba2NdNb1-xSbxO6. In the second part of this project the compounds in the series Ba2LnSnxB'1-xO6-d (Ln = Pr, Nd or Tb and B' = Nb5+ or Sb5+) were examined to understand the relative stability of oxygen vacancies in these materials compared to the oxidation of the lanthanide cations and to determine if any oxygen vacancy ordering occurred. It was found, using a combination of structural characterisation, X ray Absorption Near Edge Structure and Ultra-Violet, Visible and Near Infrared spectroscopies, that with Ln = Pr or Tb increased Sn4+ doping results in a change in the oxidation state of the Ln3+ cations to Ln4+. This leads to those series containing little or no oxygen vacancies. A loss of B site cation ordering was found to accompany this oxidation state change and phase segregation was found to occur in the Ba2PrSnxSb1-xO6-d series most likely due to the Pr3+ and Pr4+ cations segregating into different phases. The Nd3+ cations in the series Ba2NdSnxSb1-xO6-d, however, can not oxidise to the tetravalent state so the number of oxygen vacancies rises with increasing x. It was found that oxygen vacancies concentrate onto the axial site of the compounds with x = 0.6 and 0.8 at ambient temperature. In Ba2Sn0.6Sb0.4O5.7 the oxygen vacancies were found to change to concentrating on the equatorial site at higher temperatures and it is suggested that this oxygen vacancy ordering plays a role in the adoption of I2/m monoclinic symmetry.

The molecular magnet [FeII(£G)FeII(£N)(ox)2(Phen)2]n, whose chemical formula is C28H16Fe2N4O8 for unity, has been studied by magnetization measurements, neutron diffraction, and field-dependent specific heat. From the magnetization measurements, the quasi-ferrimagnetic behavior at T>Tm region can be well described with alternating Land&#x00E9; factors within 1D Ising chain model. However, in T<Tm region, the construction of long-range magnetic ordering due to the increase of interchain interaction was investigated, which is consistent with the anomaly shown in the low temperature specific heat measurement. Furthermore, an intrinsic antiferromagnetic configuration is deduced from analyzing Bragg pattern of neutron scattering. In specific heat measurement, a £f-type anomaly indicating the long-range magnetic ordering was observed. In addition, the magnetic entropy due to this anomaly is much smaller than expected value indicating the spin fluctuated as short-range ordering at T>Tm.

Fundamental understanding of the structural changes occurring during hydrate formation and inhibition is important in the development of new strategies to control hydrates in flowlines and in inhibitor design. Neutron diffraction coupled with Empirical Potential Structure Refinement (EPSR) simulation has been used to determine the hydration structure around propane molecules before and during sII hydrate formation. The EPSR simulation results were generated by fitting neutron data (with H/D isotopic substitution) obtained from the SANDALS diffractometer at ISIS. Using this combination of techniques, the structural transformations of water around propane can be studied during propane (sII) hydrate formation. The hydration structure was found to be different in the liquid phases of the partially formed propane hydrate compared to that before any hydrate formation. The effect of a kinetic hydrate inhibitor, poly-N-pyrrolidone on the hydration structure was also examined. No significant effect was observed on the water structure in the presence of this inhibitor.

This project proposes a reactor-based instrument, which retains most of the above advantages of spallation source engineering instruments, while maintaining the advantages inherent to steady-state instruments. The main idea is to allow the entire white beam from the reactor onto the sample---no monochromation. Diffraction is then allowed at a fixed angle, and information from two sample directions can be obtained simultaneously. Since a white beam is incident onto the sample, the diffraction condition is satisfied for multiple sample planes in the fixed angle of diffraction. Multiple analyzer/detector pairs are placed downstream from the sample and tuned to scatter only one of the diffracted wavelength bands. Monte Carlo methods were used to create models of both a standard two-axis engineering diffractometer, found on current reactor sources, and the proposed white beam instrument. There models were validated by experiments performed on a standard two-axis instrument, which was also modified to operate in a white beam configuration, in which the position of the sample and monochromator were interchanged. Both the models and the experiments of the white beam instrument showed proof of concept for this design and identified areas of concern that required special attention. Upon a comparison on the results from the standard two-axis instrument to the results from the white beam instrument (both simulation and experimental), it was found that the standard diffractometer showed a better performance in all aspects. However, this project proposes numerous areas where the white beam design can be improved upon in order to enhance its performance as an engineering instrument. The most important of these is the design of an appropriate analyzer/detector system, as the results overwhelmingly show this to be the area of greatest concern. Ideas for a few such designs are also given. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2009-04-23 17:46:59.419

Nuclear reactor steam generator tubes, manufactured from Nickel alloys such as Inconel 690 (INC690), are potentially susceptible to failure by Stress Corrosion Cracking where crack initiation may be exacerbated by internal stress fields. A more comprehensive understanding of this potential failure mechanism was gained via an exploration of a model of INC690’s behaviour under Constrained loading conditions in compression and tension. An Elasto-Plastic Self-Consistent (EPSC) model was used to predict the lattice stresses and strains resulting from Constrained loading in INC690 for four crystallographic planes. The internal strain fields generated under such conditions were shown to be markedly different from those developed under Uniaxial loading. Finite Element Modeling was used to design tensile and compression samples as well as a testing rig that would allow the application of a compressive load along one axis of the specimen with simultaneous constraint along another and free-deformation along the third. Lattice strain measurements were done for both compressive and tensile loading using Time-Of-Flight neutron diffraction. The predicted and experimental values showed reasonable agreement; mainly in terms of crystallographic plane interaction and behaviour. Iterative computer modeling was used to achieve a more realistic depiction of the lattice strains developed. This research allowed for an extension on the Uniaxial findings by examining the material’s behaviour under more complex loading that better approximates steam generator tube operating conditions. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2010-08-31 16:19:23.331