The base metal distribution in, and losses to, Anglo Platinum six-in-line and slag cleaning furnace slags were characterised to coincide with various process changes at Waterval Smelter from 1999 to 2009. The base metals are presumed to be reliable indicators of PGE losses and are easier to detect and measure than these elements are. In addition, base metal and sulphur levels are used to monitor and control many smelter processes, including slag cleaning and converting. Some losses to slag are recoverable but others are not – these have been quantified during this study. Slag composition and smelting temperatures have varied substantially, and optimisation of the slag cleaning furnace – a first for the South African platinum industry – has produced a wide variation in oxidation conditions. Most of the base metal losses in the slag cleaning furnace are mechanically entrained matte particles, the largest of which should be recovered. These have been examined to establish any relationship between composition, size, and depth within the furnace so that recommendations can be made to limit these types of losses. In the six-in-line furnaces, over half of base metal losses to slag are as dissolved phases, which are not recoverable. Levels of dissolved metals have been measured and related to furnace operating conditions and slag composition. The prediction of such base metal losses is not easy, because the slag compositions are so complex. One aspect of the project has been to compare the measured distribution of the base metals with those calculated using the FactSage equilibrium model, to identify problem areas, and to recommend actions which could improve the predictions of this and similar modelling programs for base metal dissolution in slag. New electron microbeam techniques have been developed to quantify base metal distribution in slag, and novel combinations of these techniques with analytical chemistry and Mössbauer Spectroscopy have been pioneered. / Dissertation (MSc)--University of Pretoria, 2009. / Materials Science and Metallurgical Engineering / unrestricted

O mercado atual exige das indústrias siderúrgicas aços de melhor qualidade produzidos por meio de processos que causem menor impacto ao meio ambiente. Dessa forma, este trabalho teve como objetivo reciclar o resíduo de mármore gerado na indústria de rochas ornamentais, que possui em sua composição óxido de cálcio (CaO) e óxido de magnésio (MgO). O CaO é suficiente para substituir a cal nas escórias e o MgO contribui para a diminuição do desgaste dos refratários, através do emprego do resíduo no processo produtivo do aço. Além disso, foi realizada a substituição da fluorita por óxido de boro como fluxante na composição de misturas dessulfurantes. O resíduo de mármore foi caracterizado utilizando as seguintes técnicas: análise química via EDXFR, análise granulométrica via espalhamento de luz, área de superfície específica pelo método BET, difração de raios-X, microscopia eletrônica de varredura (MEV) e análise de micro-regiões por EDS. Visando verificar a eficiência na dessulfuração, foram formuladas misturas sintéticas utilizando a cal convencional ou resíduo de mármore, e a fluorita ou o óxido de boro. As misturas foram formuladas com o auxílio dos programas de termodinâmica computacional, Thermo-Calc e FactSage. Estas misturas foram adicionadas no aço fundido a temperatura de 1600°C sob atmosfera de argônio e agitadas por meio de um rotor de alumina. Amostras de metal foram retiradas para verificar a variação do teor de enxofre durante o experimento. O resíduo de mármore caracterizado, apresentou em sua composição 40% de CaO e 14% de MgO, na forma dos carbonatos CaCO3 e MgCO3. Obteve uma perda de massa de 42,1%, na forma de CO2 a temperatura de 780°C. Os experimentos mostraram que, as misturas testadas apresentaram, na maioria dos casos, eficiência de dessulfuração acima de 60%. / The present market requires from steel industry better quality of steel that was produced by processes that cause less impact to the environment. Thus, this study aims to recycle the marble waste generated from the industry of ornamental rocks, which has in its composition calcium oxide (CaO) and magnesium oxide (MgO). Using this waste in the steel production process, the amount of CaO is enough to replace the lime in the slag whereas the MgO contributes to reduce the wear of the refractory material. Furthermore, it was part of this study to test the replacement of the fluorite by boron oxide as desulfurizing flux into the composition of mixtures. The marble waste was characterized using the following techniques: chemical analysis (EDXFR), particle size analysis with a light scattering method, specific surface area by BET method, Xrays diffraction (XRD), scanning electron microscopy (SEM), analysis of micro-regions by energy dispersive spectroscopy (EDS) and thermogravimetry analysis (TG) with mass spectrometer coupled (MS). In order to verify the efficiency of desulfurization, mixtures were formulated using conventional lime or marble waste, and fluorite or boron oxide. The blends were prepared using the computational thermodynamics programs, Thermo-Calc and FactSage. These mixtures were added into the molten steel under an argon atmosphere and the metallic bath stirred by a rotor of alumina at the temperature of 1600ºC. Metal Samples were removed periodically in order to verify the variation of sulfur content during the experiments. The characterization of marble waste showed in its composition the amount of 40% CaO and 14% MgO in a CaCO3 and MgCO3 carbonates forms. It was also observed a mass loss of 42.1%, in the form of CO2 at a temperature of 780 ° C. The experiments showed that the tested mixtures desulfurization efficiency was above 60%, in most cases.

O mercado atual exige das indústrias siderúrgicas aços de melhor qualidade produzidos por meio de processos que causem menor impacto ao meio ambiente. Dessa forma, este trabalho teve como objetivo reciclar o resíduo de mármore gerado na indústria de rochas ornamentais, que possui em sua composição óxido de cálcio (CaO) e óxido de magnésio (MgO). O CaO é suficiente para substituir a cal nas escórias e o MgO contribui para a diminuição do desgaste dos refratários, através do emprego do resíduo no processo produtivo do aço. Além disso, foi realizada a substituição da fluorita por óxido de boro como fluxante na composição de misturas dessulfurantes. O resíduo de mármore foi caracterizado utilizando as seguintes técnicas: análise química via EDXFR, análise granulométrica via espalhamento de luz, área de superfície específica pelo método BET, difração de raios-X, microscopia eletrônica de varredura (MEV) e análise de micro-regiões por EDS. Visando verificar a eficiência na dessulfuração, foram formuladas misturas sintéticas utilizando a cal convencional ou resíduo de mármore, e a fluorita ou o óxido de boro. As misturas foram formuladas com o auxílio dos programas de termodinâmica computacional, Thermo-Calc e FactSage. Estas misturas foram adicionadas no aço fundido a temperatura de 1600°C sob atmosfera de argônio e agitadas por meio de um rotor de alumina. Amostras de metal foram retiradas para verificar a variação do teor de enxofre durante o experimento. O resíduo de mármore caracterizado, apresentou em sua composição 40% de CaO e 14% de MgO, na forma dos carbonatos CaCO3 e MgCO3. Obteve uma perda de massa de 42,1%, na forma de CO2 a temperatura de 780°C. Os experimentos mostraram que, as misturas testadas apresentaram, na maioria dos casos, eficiência de dessulfuração acima de 60%. / The present market requires from steel industry better quality of steel that was produced by processes that cause less impact to the environment. Thus, this study aims to recycle the marble waste generated from the industry of ornamental rocks, which has in its composition calcium oxide (CaO) and magnesium oxide (MgO). Using this waste in the steel production process, the amount of CaO is enough to replace the lime in the slag whereas the MgO contributes to reduce the wear of the refractory material. Furthermore, it was part of this study to test the replacement of the fluorite by boron oxide as desulfurizing flux into the composition of mixtures. The marble waste was characterized using the following techniques: chemical analysis (EDXFR), particle size analysis with a light scattering method, specific surface area by BET method, Xrays diffraction (XRD), scanning electron microscopy (SEM), analysis of micro-regions by energy dispersive spectroscopy (EDS) and thermogravimetry analysis (TG) with mass spectrometer coupled (MS). In order to verify the efficiency of desulfurization, mixtures were formulated using conventional lime or marble waste, and fluorite or boron oxide. The blends were prepared using the computational thermodynamics programs, Thermo-Calc and FactSage. These mixtures were added into the molten steel under an argon atmosphere and the metallic bath stirred by a rotor of alumina at the temperature of 1600ºC. Metal Samples were removed periodically in order to verify the variation of sulfur content during the experiments. The characterization of marble waste showed in its composition the amount of 40% CaO and 14% MgO in a CaCO3 and MgCO3 carbonates forms. It was also observed a mass loss of 42.1%, in the form of CO2 at a temperature of 780 ° C. The experiments showed that the tested mixtures desulfurization efficiency was above 60%, in most cases.

Die Arbeit befasst sich mit der thermodynamischen Modellierung des British Gas-Lurgi-Vergasungsprozesses (BGL). Es werden auftretende Schwachstellen des Prozesses analysiert und auf das Verhalten der Mineralstoffkomponenten zurückgeführt. Auf Grundlage einer Stoffbilanz sowie zahlreicher Prozessdaten (BGL-Vergaser der SVZ Schwarze Pumpe GmbH) wurde das in SimuSage erstellte Stufenmodell an Nichtgleichgewichtszustände und Transportvorgänge angepasst. Das Modell erlaubt die qualitative und quantitative Beschreibung eines Alkalikreislaufes, welcher durch KCl geprägt ist. Mit dem Modell werden wirksame Maßnahmen abgebildet, um die Anreicherung von KCl und die damit verbundenen technischen Störungen zu vermeiden.

The present study mainly focus on two parts: one was the optimization of FactSage calculation, compared with HT-XRD measurements on mineral matter behaviors during the heating of coal and blend ashes from 500 °C to 1000 °C in reducing atmosphere. The aim was to obtain the optimized input parameters and options for FactSage calculation, and the outputs should be as close as possible to HT-XRD results. The other was the application of FactSage on ash melting behaviors. Since the maximum temperature of HT-XRD measurement in laboratory was 1000 °C in reducing atmosphere, the optimized FactSage was applied to investigate the ash melting behaviors in temperature range between 600 °C and 1600 °C for coal, biomass and their blends. The FactSage calculation was optimized by investigations of several input parameters and options including the mass ratio of reactant gas amount to ash sample, solution species and compound solid species. The results obtained from the optimized calculation were much better to fit the mineral transformations measured by HT-XRD. However, there were still some differences between the results from optimized FactSage calculations and HT-XRD measurements. This is mainly due to the amorphous substances which occurred as solid phases and liquid slag in FactSage outputs but cannot be detected by HT-XRD. Besides, several factors, such as the diffusion, particle size distribution and so on, affect the actual measurements greatly but been neglected in thermodynamic calculations, which enhance the distinctions. In addition, the effects of atmosphere were investigated and the differences of mineral matter behaviors were mainly embodied in sulphur-rich minerals, iron-rich minerals and amorphous substance. For application of FactSage on ash melting behaviors, AFTs tests for coal, biomass and their blends were adopted, and the results were well investigated by ash chemical components analyzed by XRF and also equilibrium phases calculated by FactSage. Hemispheric temperature and flowing temperature were mainly dependent on the high melting point substances at high temperature, such as free CaO in HKN and SWC, SiO2 in WS and KOL. The sintering temperature was largely affected by alkali oxides, which could combine with other oxides to form low melting point substances. For blended ashes, AFTs of the blended ash of HKN and WS shown a V shape with WS addition mass ratio rising, and the minimum values of AFTs appeared at 50 wt.% WS addition. AFTs of KOL changed in a small scale when mixed with WS, due to their similar ash composition (high in SiO2). As the SWC ash contents is much less than HKN and KOL, it did not affect the AFTs much when blended with coals. Moreover, the biomass addition affection on the blended ashes AFTs were also well illustrated by the liquid phases mass fraction and also the mineral matter transformations calculated by FactSage.

O pó de aciaria elétrica é um importante subproduto da indústria siderúrgica devido ao seu alto teor de zinco. Assim, tecnologias vêm sendo desenvolvidas visando seu aproveitamento, sendo o forno Waelz a mais difundida delas atualmente. No entanto, sua operação, por contar com um forno rotativo de grandes dimensões que abriga uma infinidade de fenômenos físico-químicos, apresenta difícil previsibilidade ab initio. Por essa razão, este trabalho faz uso de uma ferramenta avançada da termodinâmica computacional, destinada à modelagem de processos, chamada SimuSage, a fim de modelar o seu comportamento. Para a criação do modelo utilizou-se também uma base de dados termodinâmicos advinda do software FactSage e a plataforma de desenvolvimento Lazarus. Com base em dados e resultados operacionais da literatura, foi possível realizar simulações nos modos adiabático e isotérmico, comparando os resultados com os da prática industrial. Constatou-se uma grande capacidade do modelo de reproduzir os resultados da literatura, mesmo quando não há muita informação para aferição dos parâmetros, gerando boa concordância com a composição química relatada dos produtos Óxido Waelz e Escória Waelz. / The electric arc furnace dust is an important by-product of the steel industry due to its high content of zinc. Thus, technologies have been developed aiming for its use, and the Waelz Kiln is the most widespread of them today. However, counting on a very large rotary kiln that houses an infinity of physico-chemical phenomena, its operation is difficult to predict ab initio. For this reason, in order to model its behaviour this work uses an advanced tool of computational thermodynamics designed to process modelling, called SimuSage. To create the model, a thermodynamic database, provided by the FactSage software, as well as a development platform, Lazarus IDE, were also used. Based on operational data and results from de literature, it was possible to perform simulations on both adiabatic and isothermal modes comparing its results with the industrial practice. A great capability of the model to reproduce results from the literature was found, even when there is not much information for the parameters calibration, generating good agreement regarding the reported chemical composition for the products, Waelz Oxide and Waelz Slag.

Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2009.

The ability to effectively join magnesium alloys to steel will facilitate increased application and use of Mg alloys in the automotive and aerospace industries where joining Mg alloys to steel in order to achieve light weight, versatile and tailored properties in one composite part is highly desirable. The current thesis details (i) the development of a laser brazing technology for joining Mg alloy-interlayer-steel dissimilar metal combinations, (ii) thermochemical analysis of phases formed at the interface of a Mg alloy-steel joint during laser brazing, (iii) the bonding mechanisms in the Mg alloy-interlayer-steel joints using Al-12Si, Ni, and Sn interlayers, and (iv) the mechanism responsible for wetting of steel by molten Mg alloy during the laser brazing. Firstly, a diode laser brazing procedure has been developed for joining AZ31B-H24 Mg alloy sheet to aluminum coated steel sheet using a AZ92 Mg alloy filler wire. The results of this study suggest that feasibility of this process depends strongly on the pre-existing Al-12Si coating layer on the steel sheet that promotes wetting of the AZ92 Mg alloy filler alloy as well as formation of a layer of θ-Fe(Al,Si)3 interetallic compound along the fusion zone-steel interface. The average joint efficiency was 29% with respect to the AZ31B-H24 Mg alloy base metal. Failure occurred when cracks propagated along the intermetallic layer. Secondly, to predict early stage phase formation in the Mg alloy-interlayer-steel system during the laser brazing process, the thermodynamic stability of precipitated phases at the Mg alloy-Ni-steel interface during laser brazing has been evaluated using FactSage thermochemical software. Assuming local chemical equilibrium at the interface, the chemical activity-temperature-composition relationships of intermetallic compounds that might form in the AZ92 magnesium alloy-Ni-steel system in the temperature range of 600-1100 °C were estimated. The addition of a Ni interlayer between the steel and the Mg brazing alloy was predicted to result in the formation of the AlNi, Mg2Ni, and Al3Ni2 intermetallic compounds at the interface depending on the local maximum temperature. This was confirmed experimentally by laser brazing of AZ31B-H24 magnesium alloy and steel sheet with a micro-layer of electro-deposited Ni using AZ92 magnesium alloy filler wire. Bonding between the magnesium alloy and the steel was facilitated by the formation of a transition layer composed of a solid solution of Ni in Fe on the steel followed by a layer of α-Mg + Mg2Ni eutectic. A band of AlNi with different morphologies also formed along the fusion zone-steel interface, but was not directly responsible for bonding. The average joint efficiency was 56.5% with respect to the AZ31B-H24 Mg alloy base metal and 94.8% higher than that of laser brazed joint using Al-12Si interlayer. Thirdly, to study a low melting point temperature interlayer element, the brazeability of AZ31B-H24 magnesium alloy sheet to Sn-coated steel sheet has been investigated. All tensile-shear specimens fractured in the steel base metal well away from the brazed joint. The results showed that while the Sn coating promoted good wetting between the molten filler alloy and the steel sheet, it did not play a role in forming the final bond. Its primary function appeared to be in maintaining a clean, oxide-free steel surface until the molten Mg filler alloy could come in direct contact with the steel surface. Bonding between the magnesium alloy and the steel was facilitated by the formation of two nano-scale transition layers composed of Fe(Al) solid solution on the steel followed by a layer of Al8Mn5 phase on top of Fe(Al) in the fusion zone along the interface. High resolution-TEM analysis showed that an orientation relationships (OR) with low angle of rotation of the matching planes and low interplanar mismatch existed at the Fe(Al)-Al8(Mn,Fe)5 interface. This was found to be responsible for the low interfacial energy density, good wetting and strong interfacial bond observed in this complex dissimilar metal system. Finally, wetting has been characterized by measuring the contact angles of AZ92 Mg alloy on Ni electro-plated steel as a function of measured peak temperature reached during laser heating. Reactions between molten Mg and Ni led to a contact angle of about 86º in the peak temperature range of 618-750 ºC (denoted as Mode I) and a dramatic decrease to about 46º in the temperature range of 824-1020 ºC (denoted as Mode II). Scanning and transmission electron microscopy (SEM and TEM) indicated that AlNi + Mg2Ni reaction products were produced between Mg and steel (Mg-AlNi-Mg2Ni-Ni-Fe) in Mode I, and just AlNi between Mg and steel (Mg-AlNi-Fe) in Mode II. From high resolution TEM analysis, the measured interplanar mismatches for different formed interfaces in Modes I and II were 17% {Mg-AlNi}-104% {AlNi-Mg2Ni}-114% {Mg2Ni-Ni} and 18% {Mg-AlNi}-5% {AlNi-Fe}, respectively. Therefore, it is suggested that the poor wettability in Mode I was caused by the existence of Mg2Ni since AlNi was the immediate layer contacting molten Mg in both Modes I and II and the presence of Mg2Ni increases the interfacial strain energy of the system. This study has clearly demonstrated that the lattice mismatching at the interfaces between reaction product(s) and substrate, which are not in direct contact with the liquid, can greatly influence the wetting of the liquid.

Coal, as energy resource, possesses numerous characteristics and properties which all have an influence on its gasification behaviour. The two properties considered critically important when evaluating a coal source for gasification are its mineral content and slagging behaviour. Research has indicated that slag formation can be inhibited or even prevented by the addition of a fluxing agent. It is thus of great importance to understand the mineral interaction during gasification, in order to select a suitable fluxing agent for the prevention of slagging and clinker formation in the gasifier. The aim of this dissertation is to evaluate the slagging properties of a coal source with the addition of iron as a fluxing agent and to study the transformation of the mineral and added iron during gasification. A pre-determined amount of elemental iron (between 2 and 20 percentage by mass) was added to three different coal samples obtained from Sasol's operations in South Africa. The transformation of the iron in conjunction with the possible iron-containing minerals present in the coal was studied by means of Mossbauer spectroscopy. Typical characterisation analyses were also carried out on the original coal samples. The ash fusion temperature analyses (AFT) were used to study the slagging behaviour of the iron-spiked coal samples. Even though AFT analyses only provide an average flow property, it gives a good indication of the changes that the iron addition induces in coal properties. FactSage modelling was carried out in conjunction with the Mossbauer and AFT analyses. The AFT analysis on all of the samples indicated that the iron addition led to a 20% decrease in the AFT of all three the coal samples. The decrease observed, can be attributed to three main reasons: Formation of lower melting iron-containing phases, bridging of oxygen bonds by FeO and Fe203and the lowering of the viscosity by the iron-oxides, mainly hematite. Mossbauer spectra of the three original coal samples indicated that pyrite was the only iron-bearing mineral present / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2009.

Coal, as energy resource, possesses numerous characteristics and properties which all have an influence on its gasification behaviour. The two properties considered critically important when evaluating a coal source for gasification are its mineral content and slagging behaviour. Research has indicated that slag formation can be inhibited or even prevented by the addition of a fluxing agent. It is thus of great importance to understand the mineral interaction during gasification, in order to select a suitable fluxing agent for the prevention of slagging and clinker formation in the gasifier. The aim of this dissertation is to evaluate the slagging properties of a coal source with the addition of iron as a fluxing agent and to study the transformation of the mineral and added iron during gasification. A pre-determined amount of elemental iron (between 2 and 20 percentage by mass) was added to three different coal samples obtained from Sasol's operations in South Africa. The transformation of the iron in conjunction with the possible iron-containing minerals present in the coal was studied by means of Mossbauer spectroscopy. Typical characterisation analyses were also carried out on the original coal samples. The ash fusion temperature analyses (AFT) were used to study the slagging behaviour of the iron-spiked coal samples. Even though AFT analyses only provide an average flow property, it gives a good indication of the changes that the iron addition induces in coal properties. FactSage modelling was carried out in conjunction with the Mossbauer and AFT analyses. The AFT analysis on all of the samples indicated that the iron addition led to a 20% decrease in the AFT of all three the coal samples. The decrease observed, can be attributed to three main reasons: Formation of lower melting iron-containing phases, bridging of oxygen bonds by FeO and Fe203and the lowering of the viscosity by the iron-oxides, mainly hematite. Mossbauer spectra of the three original coal samples indicated that pyrite was the only iron-bearing mineral present / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2009.