In the present study, the dissolution mechanism and rate of lime, limestone and dolomite in converter slag was studied. Lime dissolution in stagnant slag was studied first and dissolution of lime, limestone and dolomite under forced convection were carried out by new experimental setup. Dissolution of different CaO samples into stagnant converter slags was carried out in a closed tube furnace at 1873K. In the case of CaO-‘FeO’-SiO2 slag, the dissolution of CaO rod in the stagnant slag was retarded after the initial period (2 minutes). A dense layer of 2CaO∙SiO2 was found to be responsible for the total stop of the dissolution. It could be concluded that constant removal of the 2CaO∙SiO2 layer would be of essence to obtain high dissolution rate of lime. In this connection, it was found necessary to study the dissolution of lime in moving slag. In order to obtain reliable information of lime dissolution under forced convection, the commonly used rotating rod method was examined. Both CFD calculation and cold model experiments showed evidently that the mass transfer due to radial velocity introduced by forced convection was zero if the rod was centrally placed in a cylindrical container. A new experimental design was therefore developed. A cube was placed in the crucible and stirred by Mo rod along with slag. The whole system could be quenched in order to maintain the state of the system at high temperature. A linear relationship between normalized length and time was obtained for lime dissolution. Different lime samples showed big difference in dissolution rate. It was found that the main mechanism of CaO dissolution in slag was due to the removal of 2CaO∙SiO2 layer. Decomposition and dissolution of limestone and dolomite in slag at 1873 K were studied. The decomposition was carried out both in argon and in slag under argon atmosphere. The decomposition process was simulated using Comsol. The results showed evidently that the decomposition of limestone and dolomite was controlled mostly by heat transfer. It was also found that the decomposition of limestone product: CaO had very dense structure, no matter the sample was decomposed in slag or in argon. The slow decomposition and the dense CaO layer would greatly hinder the dissolution of lime in the slag. The present results clearly indicate that addition of limestone instead of lime would not be beneficial in converter process. Discontinuous 2CaO∙SiO2 layer along with MgO∙Fe2O3 particles was found on the surface of the dolomite sample. Some 2CaO∙SiO2 islands were found in the vicinity of the sample in the slag, which revealed therefore that the dissolution was dominated by the peeling-off of the layer of 2CaO∙SiO2-MgO∙Fe2O3 mixture. 2CaO∙SiO2, (Mg, Fe)Oss along with super cooled liquid phases were found inside dolomite sample close to the surface. 2CaO∙SiO2 phase was replaced gradually by 3CaO∙SiO2 towards the centre of the decomposed sample. / <p>QC 20120829</p>

<p>In view of the excellent mechanical, chemical and opticalproperties, AlON (Aluminum oxynitride) as well as MgAlON(Magnesium Aluminum oxynitride) have drawn the attention ofmaterials scientists in past decades. In this thesis,thermodynamic properties, synthesis and corrosion resistance tooxygen and slag of AlON and MgAlON ceramics have beeninvestigated.</p><p>Gibbs energy of AlON and MgAlON with different compositionsand temperatures were estimatedby using thermodynamicquasi-parabola rule. Phase stability diagrams of Al-O-N andMg-Al-O-N systems at different conditions have been calculated.On the basis of thermodynamic analysis, AlON and MgAlONceramics were synthesized by hot-press sintering andcharacterized by XRD, TEM and HREM analyses. An X-raydiffraction standard file of MgAlON is suggested and sent toJCPDS.</p><p>The density of AlON synthesized was 3.63g/cm³, about 97.8% of its theoretical density. Thedensity of MgAlON is 3.55 g/cm³. Fracture toughness of AlON and MgAlON is 3.96 and4.06 MPa.m^1/2. Three-point bending strength of AlON and MgAlONare 248 and 268 MPa, respectively, at room temperature andkeeps very high until 1723K. However the strength drops 189 and202 MPa for AlON and MgAlON, respectively, at 1723K. Thefracture section of AlON and MgAlON were examined and found tobe a mixed fracture of intercrystalline and cleavage fracturefor AlON and a mixed intercrystalline and transcrystallinefracture for MgAlON.</p><p>Oxidation experiments of AlON and MgAlON and a comparison ofthe oxidation behavior of AlON, MgAlON, O'SiAlON-ZrO₂and NB-ZCM have been carried out. Undernon-isothermal oxidation conditions, oxidation of AlON exhibitstwo steps with a "S"-shaped curve due to the phasetransformation of oxidation product. As temperature increases,the oxidation product, γ -Al₂O₃formed at lower temperatures will transform intoα-Al₂O₃. Due to the differences in the molar volumesbetween α-Al₂O₃and γ -Al₂O₃, cracks are likely to be formed in the productlayer promoting further oxidation. MgAlON, O'SiAlON-ZrO₂and NB-ZCM show only one step with paraboliccurves.</p><p>Isothermal oxidation experiments of AlON, MgAlON,O'SiAlON-ZrO₂and NB-ZCM have been carried out in thetemperature range of 1373-1773K. At lower temperatures, MgAlONshows the best resistance to oxidation. But at highertemperatures, such as 1773K, AlON shows the best resistance tooxidation. O'SiAlON-ZrO₂shows very good oxidation resistance in the lowtemperature range up to 1673K. But, as the temperature goes upabove 1673K, there is liquid phase produced during theoxidation process. Gas bubbles are also formed in the productlayer causing the flaking-off of some parts of the productlayer. Therefore its oxidation rate increases greatly astemperature rises to 1673K. In the case of BN-ZCM ceramics, dueto the evaporation of B₂O₃, the oxidation resistance seems to be poorest. Thechemical reaction activation energies for the initial stage ofoxidation of AlON, MgAlON, O'SiAlON-ZrO₂and BN-ZCM are 218, 330, 260 and 254 kJ/molerespectively. And the activation energies at the laterdiffusion controlling stages are 227, 573, 367 and 289 kJ/molefor AlON, MgAlON, O'SiAlON-ZrO₂and BN-ZCM respectively.</p><p>The roughness of the oxidation sample surfaces has beenmeasured by Atomic Force Microscope. As the temperatureincreases, the degrees of roughness of AlON and MgAlON surfacesincrease slightly due to the growth of crystal grain. Theroughness degree of BN-ZCM increases greatly because of theevaporation of B₂O₃. However the roughness of O'SiAlON-ZrO₂decreases as the temperature increases from 1473Kto 1673K. The main reason is that the liquid phase (glass)produced during the oxidation process at high temperatures suchas 1673K and 1773K. The roughness degree of MgAlON, AlON,O'SiAlON-ZrO₂and BN-ZCM are 234, 174, 75 and 63 nm respectivelyat 1473K, and 297, 284, 52 and 406 nm respectively at1673K.</p><p>Experiments of corrosion of AlON by CaO-MgO-"FeO"-Al₂O₃-SiO₂slags were conducted in the temperature range of1693-1753K under static conditions as well as under forcedconvection. XRD, SEM-EDS and TEM analyses on the corrodedsamples were carried out.</p><p>The results showed that the diffusion was therate-controlling step in the initial stage of the corrosion.Thereafter, the slag formation (the product layer dissolvinginto the liquid slag) became more and more important. Thisaspect was further confirmed by fractal dimension analysis ofthe interface. The overall activation energy for the corrosionprocess with slag No.1 was evaluated to be 1002 kJ. Adding"FeO" to the slag greatly enhanced the corrosion rate probablydue to the reaction of the sample with "FeO".</p><p><b>Key words:</b>AlON, MgAlON, Thermodynamics, Synthesis,Oxidation, Slag corrosion</p>

Thesis (Ph. D.)--University of Tennessee, Knoxville, 2007. / Title from title page screen (viewed on Sept. 18, 2008). Thesis advisor: C. Neal Stewart, Jr. Vita. Includes bibliographical references.

M. Tech. Metallurgical Engineering. / Aims to recover base metals (Cu, Co, Pb and Zn) that are trapped in the slag produced during copper matte smelting process in a water jacket furnace by leaching of the slag and to study the effect of the cooling rate on the leaching of the metals in acidic and in basic media.

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Geopolymer cements offer an alternative to, and potential replacement for, ordinary Portland cement (OPC). Geopolymer technology also has the potential to reduce global greenhouse emissions caused by OPC production. There is already a considerable amount of work and research conducted on geopolymers in the past decades, and it is now possible to implement this technology commercially. However, to ensure that geopolymer becomes commercially available and able to be used in the world, further understanding of its ability to provide durable and long lasting materials is required. One main property which is still relatively unexplored compared to other properties is its shrinkage properties. The objective of this thesis is therefore to examine the shrinkage of geopolymers and factors which might influence it. / The factors which influence geopolymer strength were investigated as being the factors which may influence shrinkage. The selection of the activating solution is an important factor in forming the final product of a geopolymer. Activating solution SiO2/Na2O ratio is determined to be an important influence on the shrinkage of geopolymer. SEM images of the samples enable observation of the sample topology and microstructure. An important observation was the existence of a ‘knee point’ which also occurs in OPC shrinkage. The ‘knee point’ is the point where the shrinkage goes from rapid shrinkage to slow shrinkage. From SEMs it is noted that the samples past the knee point are shown to have a smoother topology which means it is more reacted. / Autogenous shrinkage is an important issue for OPC containing a high amount of silica, and is also a key factor in geopolymer shrinkage. Autogenous shrinkage is tested by keeping samples in a sealed environment where water lost to drying is kept to a minimum. It is noted that sealing and bagging the samples reduces the shrinkage considerably. The water to cement ratio, which is an important factor in OPC shrinkage, is also explored for the case of geopolymers. Water content plays an important role in determining early stage shrinkage, and has little to no effect on the later stage shrinkage. The water loss from the samples during drying on exposure to environment is noted and compared. The addition of more water did not necessary means that more water was lost. / Addition of slag is known to be beneficial to geopolymers by giving early structural strength and faster setting time. Commercial geopolymer concrete will also include the use of slag. However, the addition of slag up to a certain extent gives a deleterious affect on shrinkage. / A different type of Class F fly ash source with different composition data was used to see its effect on shrinkage, with only a slight influence observed between the two ashes tested. Fly ash was also ground for different lengths of time before use in geopolymerization, with grinding for less than 12 hours giving higher shrinkage than an unground sample, but shrinkage the decreasing with grinding for 18 or 24 hours. This initial higher shrinkage has been attributed to the mechanism of grinding which resulted in unevenly shaped fly ash particles taking up a larger initial volume resulting in higher shrinkage. The sample grinded for 24 hours showed higher shrinkage due to the particle size to be so fine that agglomerates may have form during mixing which would result in a lower reaction rate which increases the shrinkage. Elevated curing temperatures also reduce geopolymer shrinkage. / Thus, it is clear that the shrinkage of geopolymers is influenced by a wide range of variables, and more notably by a few important variables: activating solution ratio, addition of water, grinding and bagging. The shrinkage of geopolymers can be correlated to the strength to a certain extent. However, the understanding of the shrinkage of geopolymers is still at a very initial phase, and further research is required.