This Thesis describes a study of the compaction and the sintering of ceramic powders within the context of their "near net shape forming" into dense bodies. The operation of near net shape forming is the manufacture of ceramic parts with a required external dimensional tolerance combined with a defect free internal microstructure. The current study considers these requirements by focusing upon the fundamental facets of near net shape forming operations. The effects of the processing and material parameters on the compaction behaviour of agglomerated alumina powders have been investigated experimentally. It has been shown that the green compacts, formed from the agglomerated alumina powders by the uniaxial die pressing technique, possess certain density distribution patterns due to the frictional forces during the compaction process, and these density distributions depend primarily upon the properties of the agglomerates and the lubrication state of the die wall. The density distributions in the green compacts have been determined experimentally using the coloured layer technique and predicted using a first order model. Due to the inhomogeneous density distributions in the green compacts, the shrinkage of the compacts was not homogeneous. As a result, the shapes of the sintered compacts were not geometrically linear scaled replicas of the green compacts and the shape distortions in the sintered compacts have been characterised. It has been shown that there is a relationship between the extent of the shape distortions and the density distributions in the green compacts; that is, the more inhomogeneous green compacts the more is the shape distortions in the resulting sintered compacts. Sintering and grain growth equations, modified from established relationships, have been used for the sintering simulations in order to predict both the progression of the density and grain size of the sintered compacts. In order to predict the overall shape of the sintered compacts, a first order model has been developed by combining the predicted density distributions in the green compacts and the predicted density of the sintered compacts. The extent of the shape distortions have been reduced by optimising the properties of the agglomerates and the state of the die wall lubrication condition.

No description available.

In the iron ore pelletizing, the sintering of the pellets takes place in a rotary kiln which is lined with refractory bricks. During the process, deposited materials such as iron ore slag, additives, binders and fly ash stick on the surface of the lining, and with time, by infiltration and diffusion, a corroded layer is formed. Some of the reactions occurred in that layer are promoted by the presence of alkalis. Refractory/deposited materials reactions and infiltration of deposited materials were studied at laboratory scale. In this study, techniques such as differential scanning calorimetry (DSC), x-ray diffractometry (XRD) and scanning electron microscopy (SEM) were used. Reaction temperatures, phase transformations and infiltration depth of deposited materials were determinated. Additions of alkalis into the materials involved were used to enhance the reactions between them. Using powder mixtures the results of DSC show that in addition of K2CO3 the reaction temperature range is 850-950°C showing formation of new phases around 850°C with kalsilite and around 950°C with leucite; in addition of the mixture Na2CO3 and K2CO3, there is a broader temperature interval of 600-925°C with formation of kalsilite at lower temperatures and nepheline at higher temperatures. In the characterization of the infiltration of deposited materials into the brick it was observed that nepheline was formed mainly in the corroded brick layer but K feldespathoids (leucite, kalsilite, kaliophilite) were formed beneath the corroded brick layer. / <p>Validerat; 20110705 (anonymous)</p>

O aumento da demanda por aços cada vez mais exigentes, em termos de composição química e limpidez interna, faz com que as condições de refino nas aciarias sejam cada vez mais severas. Ao mesmo tempo, o aumento dos tempos de tratamento do aço, aliado às outras variáveis operacionais como quantidades e tipos de adições químicas, etc. fazem com que haja um aumento no tempo de contato entre o revestimento refratário das panelas de transporte de aço e escórias com conseqüente redução do desempenho (vida) de tais revestimentos refratários. Apesar dos esforços no intuito de redução de custos com redução de consumos de refratários, é cada vez maior a pressão sobre os custos de produção e de segurança operacional. Neste sentido, a construção de modelos de previsão de vida em função de tais variáveis é de extrema importância para a gestão de processos e contratos, estabilidade operacional e segurança. Além disso, os estudos de post-mortem podem contribuir no sentido de compreensão física e química de tais fenômenos e mecanismos de desgaste, contribuindo assim para a validação de tais modelos determinísticos. Neste estudo, buscou-se verificar quais variáveis operacionais influem no desempenho (vida) das panelas através de correlações estatísticas. O modelamento levou em consideração os dados de 6 meses de operação da aciaria de uma usina integrada com capacidade de 4,5 Mt/ano. O estudo post-mortem realizado em uma das panelas, após o final de sua campanha, mostrou-se eficiente na validação de tais correlações e no entendimento físico e químico dos possíveis fenômenos e mecanismos de desgaste. As análises mostraram que as variáveis que impactam a vida das panelas de aço são a temperatura de vazamento do aço, temperatura do aço na panela pós vazamento, quantidade de aço chapas grossas (CG) produzido, rota de tratamento dessulfurado, tempo de panela cheia, participação do forno panela no refino secundário, condições da panela, carga de aço na panela, adições de nefelina, escória sintética, fios de cálcio silício (CaSi) e ferro alumínio cálcio (FeAlCa), ligas de manganês e tempos de tratamento no refino secundário. O estudo de post-mortem de amostras de refratário da linha de escória extraída de uma das panelas revelou que o principal mecanismo de desgaste desta região é a corrosão química pela escória que é facilitada pelas adições de nefelina. / The increased demand for increasingly demanding steels, in terms of chemical composition and internal sanity, makes the conditions of refining in steelmaking plants are increasingly stringent and select. At the same time, increasing metallurgical treatment times, combined with the various other operating variables such as the quantities and types of chemical additions, etc. makes that there is an increase in contact time between the refractory coating of steel transport ladles and slag with a consequent reduction in performance (life) of such refractory linings. Despite efforts in order to reduce costs with a reduction of refractory consumption, it is increasing the pressure on the costs of production and operational safety. In this sense, the construction of life prediction models according to such variables is extremely important for cost reduction, process management and procurement, operational stability and safety. Moreover, post-mortem studies can contribute towards chemical and physical understanding of such phenomena and wear mechanisms, thus contributing to the validation of such deterministic models. In this study, we sought to determine which operating variables really influence the performance (life) of the ladles through statistics correlations. The modeling took into account data from 6 months of operation of an integrated steelmaking plant with capacity of 4.5 Mt / year. The study post-mortem conducted on some ladles, after the end of their campaigns, was effective in the validation of such correlations and in the physical and chemical understanding of possible phenomena and wear mechanisms. The analysis showed that the variables that impact in the life of steel\'s ladles are the steel taping temperature, the steel taping temperature in the ladle after taping, amount of produced plate mill (CG) steel, desulfurized treatment route, ladle full time, participation of the ladle furnace in the secondary refining, ladle conditions, steel load in the ladle, nepheline additions, synthetic slag, calcium silicon (CaSi) and iron aluminium calcium (FeAlCa) wires, manganese alloys and treatment times in the secondary refining. The post-mortem study of slagline\'s refractory samples extracted from ladles in operation revealed that the main wear mechanism in this region is the chemical corrosion by slag and is facilitated by additions of nepheline.

O aumento da demanda por aços cada vez mais exigentes, em termos de composição química e limpidez interna, faz com que as condições de refino nas aciarias sejam cada vez mais severas. Ao mesmo tempo, o aumento dos tempos de tratamento do aço, aliado às outras variáveis operacionais como quantidades e tipos de adições químicas, etc. fazem com que haja um aumento no tempo de contato entre o revestimento refratário das panelas de transporte de aço e escórias com conseqüente redução do desempenho (vida) de tais revestimentos refratários. Apesar dos esforços no intuito de redução de custos com redução de consumos de refratários, é cada vez maior a pressão sobre os custos de produção e de segurança operacional. Neste sentido, a construção de modelos de previsão de vida em função de tais variáveis é de extrema importância para a gestão de processos e contratos, estabilidade operacional e segurança. Além disso, os estudos de post-mortem podem contribuir no sentido de compreensão física e química de tais fenômenos e mecanismos de desgaste, contribuindo assim para a validação de tais modelos determinísticos. Neste estudo, buscou-se verificar quais variáveis operacionais influem no desempenho (vida) das panelas através de correlações estatísticas. O modelamento levou em consideração os dados de 6 meses de operação da aciaria de uma usina integrada com capacidade de 4,5 Mt/ano. O estudo post-mortem realizado em uma das panelas, após o final de sua campanha, mostrou-se eficiente na validação de tais correlações e no entendimento físico e químico dos possíveis fenômenos e mecanismos de desgaste. As análises mostraram que as variáveis que impactam a vida das panelas de aço são a temperatura de vazamento do aço, temperatura do aço na panela pós vazamento, quantidade de aço chapas grossas (CG) produzido, rota de tratamento dessulfurado, tempo de panela cheia, participação do forno panela no refino secundário, condições da panela, carga de aço na panela, adições de nefelina, escória sintética, fios de cálcio silício (CaSi) e ferro alumínio cálcio (FeAlCa), ligas de manganês e tempos de tratamento no refino secundário. O estudo de post-mortem de amostras de refratário da linha de escória extraída de uma das panelas revelou que o principal mecanismo de desgaste desta região é a corrosão química pela escória que é facilitada pelas adições de nefelina. / The increased demand for increasingly demanding steels, in terms of chemical composition and internal sanity, makes the conditions of refining in steelmaking plants are increasingly stringent and select. At the same time, increasing metallurgical treatment times, combined with the various other operating variables such as the quantities and types of chemical additions, etc. makes that there is an increase in contact time between the refractory coating of steel transport ladles and slag with a consequent reduction in performance (life) of such refractory linings. Despite efforts in order to reduce costs with a reduction of refractory consumption, it is increasing the pressure on the costs of production and operational safety. In this sense, the construction of life prediction models according to such variables is extremely important for cost reduction, process management and procurement, operational stability and safety. Moreover, post-mortem studies can contribute towards chemical and physical understanding of such phenomena and wear mechanisms, thus contributing to the validation of such deterministic models. In this study, we sought to determine which operating variables really influence the performance (life) of the ladles through statistics correlations. The modeling took into account data from 6 months of operation of an integrated steelmaking plant with capacity of 4.5 Mt / year. The study post-mortem conducted on some ladles, after the end of their campaigns, was effective in the validation of such correlations and in the physical and chemical understanding of possible phenomena and wear mechanisms. The analysis showed that the variables that impact in the life of steel\'s ladles are the steel taping temperature, the steel taping temperature in the ladle after taping, amount of produced plate mill (CG) steel, desulfurized treatment route, ladle full time, participation of the ladle furnace in the secondary refining, ladle conditions, steel load in the ladle, nepheline additions, synthetic slag, calcium silicon (CaSi) and iron aluminium calcium (FeAlCa) wires, manganese alloys and treatment times in the secondary refining. The post-mortem study of slagline\'s refractory samples extracted from ladles in operation revealed that the main wear mechanism in this region is the chemical corrosion by slag and is facilitated by additions of nepheline.

Na última década, para atender à demanda de aço requerida pelo aquecimento da economia mundial, aliado ao aumento da produtividade dos altos fornos, as usinas siderúrgicas vêm enfrentando problemas de disponibilidade de equipamentos, principalmente para escoar a produção do gusa dos Altos Fornos para a Aciaria realizada por Carros Torpedo. Estudos sobre mecanismos de corrosão em refratários utilizados em carro torpedo mostraram que a presença de espinélio, MgAl2O4, melhora a resistência à erosão e à penetração de escória, em refratários de alta alumina. Considerando que a corrosão em refratários é governada pela área de interface com o metal/escória, a diminuição da porosidade dos refratários contribui para a diminuição desta área. Portanto, para que a resistência à corrosão do revestimento refratário seja melhorada, é necessário que os caminhos que conduzem à penetração do banho (gusa/escória), sejam preenchidos ao máximo, sem comprometer a microestrutura diante de possíveis variações volumétricas, resultantes de expansão térmica diferencial. O objetivo desse trabalho é avaliar o comportamento ao desgaste por corrosão gusa/escória em refratários formados a base de Al2O3/SiC/C/MgAl2O4 incorporados com espinélio de alumínio magnésio na porosidade aberta do material refratário. Para análise da formação e estabilidade química do espinélio, a partir das soluções mistas de nitratos de magnésio e alumínio foram utilizadas análises termogravimétrica, (TG), análise térmica diferencial, (DTA), difratometria de raios X, (DRX). Após as impregnações dos corpos de prova e ensaios de corrosão e escorificação, realizados em Forno Tamman foram utilizadas as técnicas de microscopia eletrônica de varredura (MEV), porosimetria de mercúrio, difratometria de raios X, DRX, para avaliar os mecanismos de desgaste do refratário. / In the last decade to get the demand of steel required for the global economy warming, coupled with the increasing blast furnaces productivity, steel mills have had problems of equipment availability, mainly to transfer hot metal productionl from blast furnaces to Steelmaking by Torpedo Cars. Studies of corrosion mechanisms in refractory materials used in torpedo cars showed that the presence of spinel, MgAl2O4, improves the erosion resistance and slag penetration in high-alumina based refractories. Considering that the refractories corrosion is controlled by the interface with the hot metal or slag, the decrease of refractories porosity contributes to the reduction in this surface area. Therefore, the refractory lining corrosion resistance improved when the pathways lead to penetration of the bath (hot metal/slag) are filled up to the maximum, without jeopardizing the microstructure, avoiding volumetric changes by differential thermal expansion. The goal of this study is to evaluate the corrosion wear behavior by hot metal/slag of Al2O3/C/SiC/MgAl2O4 based materials incorporated with aluminum magnesium spinel into open porosity of this refractory materials. Thermal analysis (TG/DTA) and X-ray diffraction (XRD) were simultaneously study used the formation and chemical stability of spinel obtained from mixed solutions of b using magnesium and aluminum nitrates. After impregnation and corrosion tests Tammann furnace materials samples were characterized by scanning electron microscopy (SEM), mercury porosimetry, X-ray diffraction (XRD) to evaluate the wear mechanisms of refractory.

A indústria siderúrgica busca continuamente melhorias no desempenho dos refratários, como forma de melhorar sua competitividade, em um mercado caracterizado pela competição global. Um dos principais fatores de desgaste dos refratários é a corrosão, que no ambiente siderúrgico, está diretamente relacionada com a qualidade das escórias, na maioria dos equipamentos. Nesse contexto, o presente trabalho apresenta um estudo dos principais fatores que desgastam quimicamente o revestimento dolomítico, com o objetivo de entender os fenômenos que estavam impactando no desempenho dos refratários utilizados na panela de aço da Siderúrgica Riograndense. Para o estudo em questão, o comportamento químico dessas escórias foi monitorado de setembro de 2008 a outubro de 2009. Para análise didática os dados foram estratificados em três períodos, onde o período 01 corresponde aos meses de setembro, outubro e novembro de 2008, período 02 englobam os meses de fevereiro a junho de 2009 e o período 03 revela os resultados de julho a outubro de 2009. Os resultados de monitoração da qualidade da escória foram apresentados por equipamento forno elétrico a arco (FEA) e forno panela (FP). Os principais parâmetros de processo avaliados, foram a basicidade binária, teor de MgO e oxidação da escória. Os resultados foram relacionados com o desempenho do revestimento refratário aplicado na panela de aço. Para a análise dos dados foi utilizado o Minitab um software que oferece um conjunto de ferramentas estatísticas. Pode-se inferir, a partir da análise dos resultados apresentados nesse trabalho, que as ações de redução da oxidação da escória do forno elétrico através de ajustes no sistema de injeção de oxigênio das injetoras, propiciaram uma redução do óxido de ferro nas escórias do forno panela, permitindo correções da basicidade binária nesse mesmo equipamento. Estas ações em conjunto com a elevação na concentração do óxido de magnésio, através da introdução de cal dolomítica no processo, promoveram melhor formação do coating no revestimento refratário. As alterações no processo de produção do aço promoveram um significativo aumento na vida média das panelas de aço desta aciaria. / The steel industry is continually seeking improvements in the performance of refractories, as a way to improve their competitiveness in a global market. A major factor in refractories wear is chemical corrosion. In the steel industry this is directly related to the quality of the slag used in most of the equipment. In this context, this work presents a study of the main factors that causes chemical wear in dolomite refractory. The main objective was the understanding of the phenomena that were impacting on the performance of refractories used in steel ladle of Siderúrgica Riograndense. For this study, the chemical behavior of slags was monitored from September 2008 to October 2009. For better understanding the analysis, the data were stratified into three periods: period 01, from September to November 2008; period 02, from February to June 2009; and the period 03, from July to October 2009 . The results of slag quality monitoring were presented separated from the electric arc furnace (EAF) and the ladle furnace (LF). The main process parameters evaluated were the binary basicity, content of MgO and oxidation of the slag. The results were correlated with the performance of refractories used in steel ladle. For the analysis of data, it was used Minitab software which offers a set of statistical tools. It can be inferred, through out the analysis of the results presented here, that the actions to decrease oxidation of the EAF slag, by adjusting the feeding system of oxygen injectors, propitiated a reduction of iron oxide in the slag of ladle furnece, which allowed corrections in binary basicity in the same equipment. These actions together with the increase in the concentration of magnesium oxide in the FP slag, through the introduction of dolomitic lime in the process, promoted the creation of a better coating on the refractory lining. The changes in the process of steel production promoted a significant increase in average life of ladle refractory in this steel making plant.

Na última década, para atender à demanda de aço requerida pelo aquecimento da economia mundial, aliado ao aumento da produtividade dos altos fornos, as usinas siderúrgicas vêm enfrentando problemas de disponibilidade de equipamentos, principalmente para escoar a produção do gusa dos Altos Fornos para a Aciaria realizada por Carros Torpedo. Estudos sobre mecanismos de corrosão em refratários utilizados em carro torpedo mostraram que a presença de espinélio, MgAl2O4, melhora a resistência à erosão e à penetração de escória, em refratários de alta alumina. Considerando que a corrosão em refratários é governada pela área de interface com o metal/escória, a diminuição da porosidade dos refratários contribui para a diminuição desta área. Portanto, para que a resistência à corrosão do revestimento refratário seja melhorada, é necessário que os caminhos que conduzem à penetração do banho (gusa/escória), sejam preenchidos ao máximo, sem comprometer a microestrutura diante de possíveis variações volumétricas, resultantes de expansão térmica diferencial. O objetivo desse trabalho é avaliar o comportamento ao desgaste por corrosão gusa/escória em refratários formados a base de Al2O3/SiC/C/MgAl2O4 incorporados com espinélio de alumínio magnésio na porosidade aberta do material refratário. Para análise da formação e estabilidade química do espinélio, a partir das soluções mistas de nitratos de magnésio e alumínio foram utilizadas análises termogravimétrica, (TG), análise térmica diferencial, (DTA), difratometria de raios X, (DRX). Após as impregnações dos corpos de prova e ensaios de corrosão e escorificação, realizados em Forno Tamman foram utilizadas as técnicas de microscopia eletrônica de varredura (MEV), porosimetria de mercúrio, difratometria de raios X, DRX, para avaliar os mecanismos de desgaste do refratário. / In the last decade to get the demand of steel required for the global economy warming, coupled with the increasing blast furnaces productivity, steel mills have had problems of equipment availability, mainly to transfer hot metal productionl from blast furnaces to Steelmaking by Torpedo Cars. Studies of corrosion mechanisms in refractory materials used in torpedo cars showed that the presence of spinel, MgAl2O4, improves the erosion resistance and slag penetration in high-alumina based refractories. Considering that the refractories corrosion is controlled by the interface with the hot metal or slag, the decrease of refractories porosity contributes to the reduction in this surface area. Therefore, the refractory lining corrosion resistance improved when the pathways lead to penetration of the bath (hot metal/slag) are filled up to the maximum, without jeopardizing the microstructure, avoiding volumetric changes by differential thermal expansion. The goal of this study is to evaluate the corrosion wear behavior by hot metal/slag of Al2O3/C/SiC/MgAl2O4 based materials incorporated with aluminum magnesium spinel into open porosity of this refractory materials. Thermal analysis (TG/DTA) and X-ray diffraction (XRD) were simultaneously study used the formation and chemical stability of spinel obtained from mixed solutions of b using magnesium and aluminum nitrates. After impregnation and corrosion tests Tammann furnace materials samples were characterized by scanning electron microscopy (SEM), mercury porosimetry, X-ray diffraction (XRD) to evaluate the wear mechanisms of refractory.

The lifetime of aluminium reduction cells is of considerable importance in the operating economics of an aluminium smelter. Not only are the cell materials costly, but cell life is also key in minimizing production downtime and the waste material generated in the cutting-out and relining of a reduction cell. This lifetime is increasingly driven by two components of the cell lining: the carbon cathode and the sidewall refractories which are the primary containment of the metal and electrolyte. Silicon nitride bonded silicon carbide (SNBSC) refractories are the current state-of-the-art sidewall materials. These materials are formed by encapsulation of SiC particles in a silicon nitride matrix, by nitridation of silicon at high temperatures under a nitrogen atmosphere. In this study the mechanisms of the corrosion of silicon nitride bonded silicon carbide refractories in an aluminium reduction cell environment were examined. Microstructural analysis of SNBSC materials by: X-ray diffraction, solid state NMR, Raman spectroscopy, XPS, and SEM, identified variations in α/β Si3N4 ratio and porosity in the binder phase, with higher porosity levels and β Si3N4 content found in the interior part of the brick. Unreacted metallic silicon was observed only as a crystalline phase inside SiC grains and is not associated with the binder phase. SNBSC samples from eight different commercial refractory manufacturers were tested in an industrial aluminium cell environment, both by immersion in industrial cells and in the laboratory. The samples showed extensive attack and considerable differentiation between the samples. The effects on the corrosion rate of porosity levels, amount of binder, α/β Si3N4 ratio, free Si content in the binder, and different factors in the environment were examined in the laboratory scale trials. A laboratory scale testing rig with some novel features, such as a rotating anode, was developed to examine corrosion resistance of samples under electrolysis conditions in molten cryolite at up to 1000oC. Corrosion test results, supported by thermodynamic calculations, identified the Si3N4 binder as the reactive phase in SNBSC materials, especially in the gas phase above the bath level. High porosity levels and high β Si3N4 fraction in the binder showed a statistically significant contribution to the corrosion rate in lab-scale corrosion trials. Commercial materials are also highly inhomogeneous in the distribution of the β Si3N4 phase as mentioned above, which complicates sample selection and the interpretation of corrosion test results. The crystal morphology of β Si3N4 is suggested as the reason for the high reactivity of these materials. This morphology characterised by elongated rod-like shape crystals with hexagonal cross section, presents a higher surface area compared to α Si3N4 crystals containing mainly flat matte crystals. In the light of this observation, the binder phase in selected samples was deliberately modified to convert a significant fraction of the α Si3N4 to β Si3N4. Corrosion rates measured from these modified samples in general support the argument that the crystallographic form of silicon nitride contributes to corrosion rate. The proposed corrosion mechanism for SNBSC materials in the aluminium reduction cell atmosphere is based on combination of oxidation of the binder followed by attack of corrosive gases to produce volatile SiF4. Thus the binder phase is initially passivated below the electrolyte level on the sidewall, where exposure to corrosive gases is limited, but occurs more rapidly in the area above the electrolyte/air interface. The intrusion of electrolyte into the refractory and capillary transport up the sidewall is a key in accelerating this reaction.

The lifetime of aluminium reduction cells is of considerable importance in the operating economics of an aluminium smelter. Not only are the cell materials costly, but cell life is also key in minimizing production downtime and the waste material generated in the cutting-out and relining of a reduction cell. This lifetime is increasingly driven by two components of the cell lining: the carbon cathode and the sidewall refractories which are the primary containment of the metal and electrolyte. Silicon nitride bonded silicon carbide (SNBSC) refractories are the current state-of-the-art sidewall materials. These materials are formed by encapsulation of SiC particles in a silicon nitride matrix, by nitridation of silicon at high temperatures under a nitrogen atmosphere. In this study the mechanisms of the corrosion of silicon nitride bonded silicon carbide refractories in an aluminium reduction cell environment were examined. Microstructural analysis of SNBSC materials by: X-ray diffraction, solid state NMR, Raman spectroscopy, XPS, and SEM, identified variations in α/β Si3N4 ratio and porosity in the binder phase, with higher porosity levels and β Si3N4 content found in the interior part of the brick. Unreacted metallic silicon was observed only as a crystalline phase inside SiC grains and is not associated with the binder phase. SNBSC samples from eight different commercial refractory manufacturers were tested in an industrial aluminium cell environment, both by immersion in industrial cells and in the laboratory. The samples showed extensive attack and considerable differentiation between the samples. The effects on the corrosion rate of porosity levels, amount of binder, α/β Si3N4 ratio, free Si content in the binder, and different factors in the environment were examined in the laboratory scale trials. A laboratory scale testing rig with some novel features, such as a rotating anode, was developed to examine corrosion resistance of samples under electrolysis conditions in molten cryolite at up to 1000oC. Corrosion test results, supported by thermodynamic calculations, identified the Si3N4 binder as the reactive phase in SNBSC materials, especially in the gas phase above the bath level. High porosity levels and high β Si3N4 fraction in the binder showed a statistically significant contribution to the corrosion rate in lab-scale corrosion trials. Commercial materials are also highly inhomogeneous in the distribution of the β Si3N4 phase as mentioned above, which complicates sample selection and the interpretation of corrosion test results. The crystal morphology of β Si3N4 is suggested as the reason for the high reactivity of these materials. This morphology characterised by elongated rod-like shape crystals with hexagonal cross section, presents a higher surface area compared to α Si3N4 crystals containing mainly flat matte crystals. In the light of this observation, the binder phase in selected samples was deliberately modified to convert a significant fraction of the α Si3N4 to β Si3N4. Corrosion rates measured from these modified samples in general support the argument that the crystallographic form of silicon nitride contributes to corrosion rate. The proposed corrosion mechanism for SNBSC materials in the aluminium reduction cell atmosphere is based on combination of oxidation of the binder followed by attack of corrosive gases to produce volatile SiF4. Thus the binder phase is initially passivated below the electrolyte level on the sidewall, where exposure to corrosive gases is limited, but occurs more rapidly in the area above the electrolyte/air interface. The intrusion of electrolyte into the refractory and capillary transport up the sidewall is a key in accelerating this reaction.