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M. Tech. Polymer Technoliogy. / Studies the basic curing, rheological and thermomechanical behaviours of hybrids composed of a VE resin and acrylated epoxidised soyabean oil (AESO). The hybrid systems were cured by free radical initiated radical copolymerisation with styrene. The prospective outcomes were: To find suitable initiators/accelerators for the VE/AESO hybrids which work within the entire composition range? To contribute to the selection of VE resins for AESO modification To establish the optimal quantity of AESO required obtaining the best cure characteristics, the most acceptable reduction in Tg, and stiffness as compared with the parent VE resin.

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

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 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.

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Thesis (M. S.)--Mechanical Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Dr. Richard W. Neu; Committee Member: Dr. David L. McDowell; Committee Member: Dr. W. Steven Johnson.