A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Engineering Johannesburg, 11 October 2016 / Refractory lining failure of damaged magnesia bricks and used alumina bricks was investigated by XRF, XRD, SEM-EDS analysis and computational thermochemistry (phase diagrams). In addition, the effect of oxygen partial pressure towards the refractory lining and alkali sulphate ratio were also determined. The presence of low melting phases of KCl, (Na, K) Cl, K2SO4 and CaSO4 compromised the refractoriness of the magnesia bricks because they are liquid at temperatures below clinkerisation temperature (1450 °C). Sodium oxide and potassium oxide in the kiln feed and chlorine and sulphur in the kiln gas atmosphere migrated into the magnesia brick and react to form KCl, (Na, K) Cl and K2SO4. Components of the magnesia brick, CaO reacted with the excess sulphur in the kiln gas atmosphere forming CaSO4. The presence of these impurity phases indicated that the magnesia bricks suffered chemical attack. Potassium and part of components of high-alumina brick reacted to form K2 (MgSi5O12) impurity phase. Phase diagram predictions indicated that the presence of sodium at any given concentration automatically results in liquid formation in the high alumina brick. This confirms that the chemical attack is also the cause of the failure of the high alumina brick. The analysis of the microstructures of both unused and damaged magnesia bricks revealed that the fracture was predominantly intergranular whereas, in high alumina brick, the fracture was transgranular. The absence of evidence of micro-cracks in both magnesia and alumina bricks rules out thermal shock as a failure mechanism. The absence of clinker species and phases in the examined magnesia and alumina bricks indicated that corrosion by clinker diffusion was absent. The partial pressure of oxygen is low (1.333×10−4 atm), it indicates the stability of Fe3O4 and Mn3O4 and therefore does not favour the oxidation of Fe3O4 to formation of Fe2O3 and Mn3O4 to formation of Mn2O3. The values of alkali sulphate ratio indicated that the kiln operating conditions were favourable for chemical attack to occur. / MT2017

Les systèmes de protection thermique ablatifs, couramment utilisés dans l'industrie de l'aérospatiale sont généralement des matériaux composites, dont la dégradation permet d'isoler thermiquement les éléments subissant des flux aérothermiques sévères. On recense dans la littérature de très nombreux systèmes, tant en terme de matrice que de type de renfort. Face à la diversité des matériaux existants et la multiplicité des sollicitations auxquelles ils peuvent être soumis, il est aujourd'hui nécessaire d'acquérir une meilleure connaissance de l'influence de la composition (matrice, renfort et porosité) de ces matériaux sur leur comportement thermique et leur tenue à l'ablation. La démarche scientifique des travaux s'articule autour d'un volet expérimental et du développement d'un modèle numérique. La caractérisation expérimentale a été construite en trois étapes, explorant chacune le comportement des matériaux à une échelle différente : le comportement thermo-chimique a été caractérisé par des essais d'ATG, de TMA et de DSC, le comportement thermique a été évalué grâce à un banc muni d'une torche oxygène acétylène. Enfin, la tenue des matériaux à un jet aérothermique sévère a été testée sur un banc d'essai équipé d'un minipropulseur. Ce dernier banc permet de tester des échantillons de plusieurs dizaines de centimètres de large et d'étudier l'impact couplé de la thermique et de l'aérodynamique. En parallèle, un modèle numérique simple simulant l'ablation a été développé et validé. L'ensemble de ces travaux ont notamment permis de mettre en évidence les liens existants entre les propriétés thermo-physiques et la tenue à l'ablation d'un matériau composite. Appuyée par des observations microscopiques des matériaux dégradés, l'étude combinée des résultats aux différentes échelles a permis de proposer des scénarii de dégradation pour chacun des matériaux. Les principaux paramètres pilotant l'avancée d'un front d'ablation ont été identifiés, l'impact primordial de la porosité a notamment été démontré. / Ablative thermal protection systems, commonly used in space industry, are usually made of composite materials. The degradation of these materials in surface allows to protect essential parts against severe aerothermal fluxes. In the literature, lots of different systems are described they are constituted of different type of matrix and reinforced by several kind of fibers. The diversity of the existing thermal protection systems raises the question of the influence of the composition of the materials on the thermal and ablative performances. The developed scientific approach is based on an experimental procedure coupled with the development of a numerical simulation. The material characterization is based on three experimental steps : the thermo-chemical behavior of the materials is investigated with TGA, TMA and DSC experiments, the thermal behavior under a severe flux is evaluated by an experimental bench equipped with an oxyacetylenic torch ; finally, the ablative behavior is characterized with a small jet-nozzle impacting the sample with a severe aerothermal flux. In parallel to the experimental characterization, a numerical simulation modeling of the ablative and thermal behavior of composite materials is developed. Links existing between the thermal behavior and the ablation resistance have been demonstrated. Degradation scenarios have been proposed thanks to the combined analysis of the experimental results at each stage of the characterization. Parameters controlling the ablation have been identified, the major impact of the porosity has been particularly demonstrated.

This thesis details an investigation into the properties and applications of shape memory alloy (SMA) composites. SMA-composites are a new material which have the possibility of having a large impact on what the structures as we know today, are constructed with. SMA-composites are adaptive materials which can be used to control the shape and frequencies of vibration of a structure. In order to determine the effectiveness of such a material, research into the functional properties of SMAs and SMA-composites was conducted. As an initial step, the transformation behaviour of constrained SMAs was investigated in order to obtain a better understanding into the recovery stress generation of these wires when embedded into a composite material. It is known that the transformation is based on two types of martensite within the alloy; self accommodating and preferentially oriented martensite. The amounts of each type and how they vary with differing pre-strain were determined through DSC measurements and an explanation for why preferentially oriented martensite is not observed during DSC testing was made. The next step was to investigate the effectiveness of embedding SMA wires into composites and the thermomechanical properties of the SMA wires and the SMA-composites were determined. This was completed using a specially designed tensile testing machine which was capable of having the whole specimen immersed into an oil bath and heated and cooled repeatedly. The stress-strain, strain-temperature, stress-temperature, resistance-strain and cyclic properties of various wires were obtained, giving a better understanding of the behaviour of SMA wires under different test conditions. NiTiCu SMA wires were embedded into kevlar composite materials and the recovery stress generation (stress-temperature), stress-strain, and strain-temperature behaviour was determined. If SMA-composites are to be used as new materials for structural applications, verification that the embedment of pre-strained SMA wires into the material doesn't adversely affect the impact behaviour needs to be carried out. SMA-composite specimens with varying volume fractions of superelastic SMA wires, pre-strain and position through the thickness were made up for impact damage characterisation. These specimens were impacted at three different energy levels. The results showed that by embedding SMA wires into composite materials there is a reasonably low damage accumulation after impact. There is also no adverse impact effect on the structure compared with structures without wires as well as structures with other types of wires such as steel and martensitic SMA wires. The SMA-composites showed good damping and energy absorption capabilities. A novel application of SMA-composites is their use as a SMA patch in order to repair damage in existing cracked metallic structures. An analytical study and finite element modelling showing the closure stresses obtainable for use as patches was made.

Black liquor recovery boilers experience significant fire-side fouling problems due to the deposition of entrained particulate matter. Increased understanding of the mechanisms by which particles deposit on these surfaces will lead to more effective management of the resultant problems. There is some evidence which suggests that the sub-micron fraction of this particulate matter deposits by thermophoresis. In an effort to determine conclusively if this is the case, a facility (the Multifuel Combustor at Sandia National Laboratories) was used which could generate and deposit fly ash under conditions that mimic those found in full scale recovery boilers, and dynamically monitor deposit growth rates. Experiments where both the deposit thickness and surface temperature were monitored in situ resulted in linear deposit growth rates despite highly non-linear surface temperature increases. This rules out thermophoresis as the dominant deposition mechanism since it is dependent on the changing thermal driving force. The morphology of the windward side deposit indicates an inertially-dependent mechanism is at work in spite of the size of the particles, which are considerably smaller than what would be commonly considered inertially impacting particles. Leeward side deposits also grow linearly, indicating that thermophoresis, although possibly contributing to deposition, is not the rate-controlling mechanism. Deposition efficiencies fell in the range of 5-15%. The morphology of the sub-micron deposits is highly structured and dendritic in appearance, with over 90% voidage. The particles form long strings or filaments which grow in parallel, indicating that the particles have a high sticking efficiency and do not roll or settle subsequent to impacting. There is minimal contact between adjacent filaments. Recently published research confirms the presence of particles in the 1-50 micron range in recovery boilers. Deposition experiments were performed on this size range as well. Termed Intermediate-size, these particles deposit many times more efficiently, and produce linear deposit growth rates just as the sub-micron particles. They also deposited in clusters of filaments which grew rapidly upward and slowly outward until the adjacent clusters merged. However in this size range the clusters tended to branch out more rapidly than the sub-micron deposits. Deposition efficiencies fell in the range of 40-65%. / Graduation date: 1999

The effect of thermo-mechanical processing by deformation and annealing on the grain boundary configuration of commercially pure Ni-200 is reported in this thesis. Ni-200 is unalloyed, thus avoiding the complex effects associated with alloying elements on the formation and development of different types of grain boundaries. One step strain-recovery with strain levels in the range of 3% to 7.5% (with 1.5% intervals) and annealing temperatures in the range of 800ºC to 1000ºC (with 100ºC intervals) were used in processing. The effects of parameters such as strain level, annealing temperature, annealing time and grain growth on grain boundary configurations were studied. Using Orientation Image Microscopy (OIM) it was found that the Fsp (fraction of special grain boundaries) value of strained samples annealed in the range of 800ºC to 1000ºC began to increase after a critical length of time, after which the Fsp value increased quickly and becoming a maximum in 2~4 minutes. The length of the critical annealing time for the increase of Fsp was shorter in the material with the higher levels of strain at a constant annealing temperature. Also the critical annealing time was shorter when annealed at higher temperatures under a fixed level of strain. The Fsp value increased to 80% from an as received value of about 30% in the samples with varying strain levels. However, the Fsp values only increased from 30% to 45% in the material without strain. Due to grain boundary migration, the Fsp values increased with grain size and became a maximum during the heat treatment of the strained material. In the material without strain however even when grain growth occurred, limited improvement in Fsp values occurred showing that contribution of strain is very important to the formation of special boundaries. By varying the strain levels, annealing temperatures and times, material with high Fsp values in a wide range of grain size can be obtained. Under the present processing conditions used however, multi-cycle was not helpful to the improvement of Fsp. TEM observations indicated dislocation tangles occurred near the grain boundary of the 1x6% strained samples. These dislocation tangles decreased with time at 800˚C and were reduced considerably after 20 minutes. Thermodynamic and kinetic models were used in the calculations of twin density-grain size relationships. The results indicated that the contribution of strain is equivalent to the increase of grain boundary energy, which provided an extra driving force and improved probability of twin embryo formation. / February 2009

This book has the introduction of the friction stir welding and friction stir processing, and introduces the newest development in FSW.Finding out the appropriate paraments of the grain size refinement in AZ31 Mg. The relationship between the resulting grain size and the applied working strain rate and temperature for the friction stir processing in AZ31 Mg is systemically examined. The Zener-Holloman parameter is utilized in rationalizing the relationship. The grain orientation distribution is also studied using the X-ray diffraction.

The stresses and the elastic constants of bcc sodium are calculated by molecular dynamics (MD) for temperatures to T = 340 K. The total adiabatic potential of a system of sodium atoms is represented by a pseudopotential model. The resulting expression has two terms: a large, strictly volume-dependent potential, plus a sum over ion pairs of a small, volume-dependent two-body potential. The stresses and the elastic constants are given as strain derivatives of the Helmholtz free energy. The resulting expressions involve canonical ensemble averages (and fluctuation averages) of the position and volume derivatives of the potential. An ensemble correction relates the results to MD equilibrium averages. Evaluation of the potential and its derivatives requires the calculation of integrals with infinite upper limits of integration, and integrand singularities. Methods for calculating these integrals and estimating the effects of integration errors are developed. A method is given for choosing initial conditions that relax quickly to a desired equilibrium state. Statistical methods developed earlier for MD data are extended to evaluate uncertainties in fluctuation averages, and to test for symmetry. The fluctuation averages make a large contribution to the elastic constants, and the uncertainties in these averages are the dominant uncertainties in the elastic constants. The strictly volume-dependent terms are very large. The ensemble correction is small but significant at higher temperatures. Surprisingly, the volume derivatives of the two-body potential make large contributions to the stresses and the elastic constants. The effects of finite potential range and finite system size are discussed, as well as the effects of quantum corrections and electronic excitations. The agreement of theory and experiment is very good for the magnitudes of C₁₁ and C₁₂. The magnitude of C₄₄ is consistently small by ∼9 kbar for finite temperatures. This discrepancy is most likely due to the neglect of three-body contributions to the potential. The agreement of theory and experiment is excellent for the temperature dependences of all three elastic constants. This result illustrates a definite advantage of MD compared to lattice dynamics for conditions where classical statistics are valid. MD methods involve direct calculations of anharmonic effects; no perturbation treatment is necessary.

M. Tech. Engineering: Chemical. / Aims to establish the cure kinetics of the thermosetting systems through the use of rheology and differential scanning calorimetry. Dynamic mechanical and thermal mechanical analyses will be used to ascertain the mechanical properties. The resistance to thermal degradation will be determined by thermogravimetric analysis.

The low cycle thermo-mechanical fatigue of laser beam welded conventionally cast Inconel 738, directionally solidified René 80 and single crystal René N5 has been evaluated. Results have been compared to gas tungsten arc and baseline alloy conditions. Metallographic examination of laser beam welds and the associated heat affected zone were conducted by scanning electron microscopy and energy dispersive spectroscopy. The impact of laser beam welding on thermo-mechanical fatigue properties of Inconel 738, René 80 and René N5 has been evaluated and recommendations for improvements and areas of further research have been presented.

The low cycle thermo-mechanical fatigue of laser beam welded conventionally cast Inconel 738, directionally solidified René 80 and single crystal René N5 has been evaluated. Results have been compared to gas tungsten arc and baseline alloy conditions. Metallographic examination of laser beam welds and the associated heat affected zone were conducted by scanning electron microscopy and energy dispersive spectroscopy. The impact of laser beam welding on thermo-mechanical fatigue properties of Inconel 738, René 80 and René N5 has been evaluated and recommendations for improvements and areas of further research have been presented.