Made available in DSpace on 2016-06-02T19:10:01Z (GMT). No. of bitstreams: 1 2601.pdf: 5587826 bytes, checksum: 717a8aef3900d3dc9c6e48239028afeb (MD5) Previous issue date: 2008-04-04 / The evolution of the world-wide production of steel in rates superior to 7% per year in the last five years, strongly driven by China, which got off 222,4 millions in 2003 for 489,0 million tons in 20071, leads to a strong increase in the demand of iron ore. Therefore, fine ore price of Carajás for Asia went out from 28,14 in 2003 for 73,20 US$ cents for unity of iron in 2007. An increase of 160%. These facts, when related to the layer exhaustion and the growing environmental pressures on Iron and Steel Plants of the whole world, have been taking to a series of studies to the use of the residues bearers from iron produced in these factories. Up to that time, there has not been consolidated any technology which is technically and economically viable for the recycling of these residues so far. The present work is about the usage of the blast furnace mud, the mill scale and the iron oxide produced in the pickling lines of Companhia Siderúrgica Nacional (CSN) in self reduction pellets shape. It starts the productions in scale laboratorial and industrial after the chemical and physical characterizations from these raw materials. As soon as the most appropriated formulation was defined, the production in experimental scale began. These tests were carried out in the residues palletizing pilot plant, developed by CSN. There were also tests of self reduction and of meltreduction. In the first one, the formation of a metal drop inside a hallow sphere was obtained, and in the second one a metal profit of 99,1%. In sequence, the alternatives were valued for internal recycling of these pellets. The use of the heat contained in the empty hot-metal torpedo-cars for self-reduction showed the most economical route. This technology of recycling was introduced industrially in CSN. Thus, in the present work of doctorate, it was developed an unpublished route for industrial recycling for iron and steel residues, which was technically and economically feasible. / O crescimento da produção mundial de aço bruto em taxas superiores a 7% ao ano nos últimos cinco anos, fortemente impulsionado pela China, que saltou de 222,4 milhões em 2003 para 489,0 milhões de toneladas em 20071, gerou um forte aumento na demanda de minério de ferro. Com isso, o preço do minério fino de Carajás para a Ásia saiu de 28,14 em 2003 para 73,20 US$ cents por unidade de ferro em 2007. Um aumento de 160%. Estes fatos, associados à exaustão das jazidas e as crescentes pressões ambientais sobre as Siderúrgicas de todo o mundo, têm levado a uma série de estudos para o aproveitamento dos resíduos portadores de ferro gerados nestas Usinas. Até então, não se consolidou nenhuma tecnologia viável técnica e economicamente para esta reciclagem. O presente trabalho trata da utilização da lama de alto-forno, da carepa de laminação e do óxido de ferro gerado nas linhas de decapagem da Companhia Siderúrgica Nacional CSN na forma de pelotas auto-redutoras. Após as caracterizações químicas e físicas destas matérias-primas, partiu-se para as produções em escala laboratorial e industrial. Definida laboratorialmente a formulação mais adequada, partiu-se para a produção experimental. Esta foi realizada na planta piloto de pelotização de resíduos, desenvolvida pela CSN. Foram realizados ensaios de auto-redução e de fusão-redução. No primeiro, o resultado foi a formação de uma gota metálica dentro de uma esfera oca e no segundo, um rendimento metálico de 99,1%. Em seqüência, foram avaliadas as alternativas para reciclagem interna destas pelotas. A utilização do calor contido nos carrostorpedo vazios para a auto-redução se mostrou como a rota mais econômica. Esta tecnologia de reciclagem já se encontra implantada industrialmente na CSN. Portanto, no presente trabalho de doutoramento, desenvolveu-se uma rota inédita de reciclagem industrial dos resíduos siderúrgicos portadores de ferro, viável técnica e economicamente.

Generation of wastes in the form of liquid, solid or gas is inevitable in any industry.Industrial Solid Waste is the waste that is generated from an industrial or manufacturing process and includes the waste generated from non-manufacturing activities as well.Most of these wastes fall under the category of Ashes, Slagsor Sludges. For the present work, three types of secondary lead slag, two types of granulated blast furnace slag (GBS) or iron slag and four types of steel slags were procured and studied.An elaborate study on various characteristics of the slags has been performed. Based on the results, all the possible applications for the individual slags are considered. The performance of the secondary lead slag as an embankment material was analyzed. The slope stability for various conditionswas analyzed using Geo5 and experimentally determined strength parameters. It was found that the material can be used safely for embankment constructions.The CBR values were very good in the range for both GBS and steel slag,thus repeated load triaxial test are done to determine the resilient modulus. k1-k3model was adopted and the regression coefficients were determined. Based on the results the pavement design is done using KENPAVE software. An exercise has been performed to determine the quantity of the conventional material that could be saved, considering the type and size of the pavement. For the aggregate sized steel slag, the tests were done to find the suitability of the material for various applications like, as railway ballast, concrete aggregate, gabion and rip rap stones. And the tests result shows the material to be suitable for these applications and is expected to perform well. Study on morphological parameters reveals that the size and gradation of any material plays an important role in its mechanical behavior, however in the case of slags, this could be tailor made by using appropriate crushers, as per the requirements.

A reação álcali-agregado é uma manifestação patológica diretamente ligada à seleção dos materiais (cimento, agregados miúdo e graúdo, água e aditivos) que pode comprometer a durabilidade das estruturas de concreto, uma vez que a interação desses materiais e as condições ambientais é que vão conferir ao concreto determinadas propriedades ligadas à sua vida útil. A reação entre os hidróxidos alcalinos solubilizados na fase líquida dos poros dos concretos e alguns agregados reativos é lenta e resulta em um gel que, ao se acumular em vazios do concreto e na interface pasta-agregado, na presença de água, se expande, exercendo pressão interna no concreto. Ao exceder a resistência à tração do concreto, a pressão interna pode promover fissurações. A reação álcali-agregado requer a atuação conjunta de água, agregado reativo e álcalis. Sua prevenção pode ser feita a partir da eliminação de um dos fatores, ou seja, a partir do emprego de agregados inertes ou de cimentos com baixos teores de álcalis ou isolamento da umidade. Na impossibilidade de eliminar um dos fatores, medidas preventivas devem ser tomadas para o emprego de agregados reativos em obras de construção civil. Entre essas, destacam-se a utilização de cimentos com baixos teores de álcalis ou a de cimentos com adições ativas mitigadoras da reação álcali-agregado: escória de alto-forno, cinza volante, metacaulim e sílica ativa, que foi o objeto de pesquisa do presente trabalho. No programa experimental foram analisados dois tipos de agregado potencialmente reativos com os hidróxidos alcalinos: EDVDOWR e PLORQLWR_ JUDQtWLFR. O primeiro, proveniente de rocha ígnea, tem como constituintes deletérios vidro, clorofeíta, calcedônia (sílica criptocristalina), que dará origem à reação do tipo iOFDOL_VtOLFD. O agregado milonito granítico provém de rocha metamórfica, tem como constituintes deletérios quartzo microgranular, quartzo recristalizado, quartzo com extinção ondulante e quartzo e feldspato deformados, que dará origem ao tipo de reação iOFDOL_VLOLFDWR. Com o objetivo de avaliar a eficiência de adições ativas em mitigar as reações, os agregados foram combinados com 16 cimentos com adições ativas. Escória de alto-forno foi adicionada a 15%, 30%, 45% e 60% e cinza volante, a 10%, 15%, 25% e 35%, teores normalmente encontrados nos cimentos brasileiros. Metacaulim foi adicionada a 5%, 10%, 15% e 20%, e sílica ativa, a 5%, 10% e 15%, teores representativos da faixa normalmente adicionada diretamente a concretos. Todos os materiais utilizados foram caracterizados química, física e mineralogicamente, incluindo a análise petrográfica dos agregados. As barras de argamassa foram analisadas ao MEV, microscópio óptico de luz transmitida, realizaram-se ensaios de porosimetria por intrusão de mercúrio e análises térmicas para quantificar a teor de portlandita residual, e determinou-se o teor de álcalis dentro das barras após a realização dos ensaios para verificar a migração de íons de sódio. Os resultados indicam que a eficiência das adições ativas varia de acordo com a composição química e mineralógica das adições, da proporção desse material no cimento, e do grau de reatividade do agregado. / The alkali-aggregate reaction is a pathologic manifestation that can induce the premature distress and loss in serviceability of concrete structures affected. It is directly associated to the selection of materials (cement, coarse and fine aggregates, water and additives), as the interaction between these materials and environmental condition will grant the concrete some of the properties related to its service life. The slow reaction between alkali hydroxides soluble in the liquid phase within concrete pores and reactive aggregates gives rise to a gel that piles up within concrete voids and the aggregate-paste interface. In presence of water, the gel expands and exerts internal pressure in the concrete. When the internal pressure exceeds the tensile strength, cracking may come up as result. The alkali-aggregate reaction requires the action of water, reactive aggregate and alkalis altogether. Prevention can be carried out by eliminating one of these factors, i.e. employing either inert aggregates or lowalkali cements, or keeping the concrete away from moisture. Otherwise, preventive measures must be taken when reactive aggregates are used in civil construction works, such as the use of low-alkali cements or composite cements bearing alkaliaggregate- reaction mitigating admixtures: blast-furnace slag, fly ash, metakaolin and silica fume, which are the object of the present research. The experimental work included the analysis of two potentially reactive aggregates to alkali hydroxides: basalt and granite milonite. The igneous basalt carries deleterious constituents such as glass, chloropheite (cryptocrystalline silica), that will give rise to the DONDOL_VLOLFD type reaction while the metamorphic granite milonite carries micro granular, recrystallized, undulate-extinction-bearing quartz and deformed feldspar grains, that give rise to DONDOL_VLOLFDWH type reaction. Aiming at evaluating how efficient in mitigating these reactions the active admixtures are, these aggregates were mixed with 16 composite cements. The contents of admixtures followed those usually found in Brazilian industrial cements for blast-furnace slag (15%, 30%, 45%, 60%) and fly ash (10%, 15%, 25%, 35%), and those generally added directly to concrete for metakaolin (5%, 10%, 15%, 20%) and silica fume (5%, 10%, 15%). All materials were characterized for their chemical composition, physical properties and mineralogy. Petrography was carried out on the aggregates. The mortar bars were analyzed at the scanning electronic and transmitted-light optical microscopes. Mercury-intrusion porosimetry and thermal analyses were carried out to quantify residual portlandite. The alkali content within the bars was determined in order to verify migration of Na+ ions. The results show that the efficiency of active admixtures varies according to their chemical and mineralogical composition and proportioning in cement, and to the aggregate reactivity.

O objetivo desta tese foi o estudo da influência do aditivo redutor de retração (SRA) e o aditivo compensador de retração (SCA) em argamassas e pastas de cimento de escória ativada com silicato de sódio. A metodologia foi centrada na análise da retração por secagem e autógena, com o estudo de outras características que influenciam no fenômeno da retração, como as propriedades mecânicas. Para o avanço no conhecimento do efeito dos aditivos no comportamento do cimento de escória, foi caracterizada a microestrutura com a determinação da análise por termogravimetria, porosimetria e difração de raios X. Neste estudo foram empregados os seguintes teores de aditivo, porcentagem relativa à massa de aglomerante: 0,5%, 1%, 1,5% e 2% do aditivo SRA e 5%, 10% e 15% do aditivo SCA. Para a análise da influência da relação a/agl foram empregadas três teores: 0,40, 0,48 e 0,56. No estudo das amostras de referência, sem a utilização de aditivo, observou-se que o aumento da relação a/agl causa o aumento da retração por secagem e da retração autógena do cimento de escória ativada. A diminuição da resistência mecânica com o aumento da relação a/agl, o que torna o esqueleto sólido mais susceptível à deformações, e o aumento das tensões capilares, em razão do aumento da quantidade de água livre para ser evaporada, são os principais fatores para o aumento da retração por secagem. No caso da retração autógena, seu aumento é atribuído ao aumento da auto-secagem com o aumento do volume de poros com diâmetro na faixa de mesoporos, além da diminuição da resistência mecânica. O aditivo redutor de retração (SRA) conseguiu reduzir a retração por secagem em percentuais de 40% até 74% aos 28 dias, no entanto, este tipo de aditivo não obteve êxito no combate a retração autógena. Com relação à resistência mecânica, o aditivo SRA causou a redução de até 40%, efeito atribuído à diminuição do grau de hidratação e retardo do refinamento da porosidade. O aditivo compensador de retração (SCA) amenizou a retração por secagem e a retração autógena, reduzindo em até 64% e 70%, respectivamente, porém reduziu em até 60% a resistência mecânica do cimento de escória ativada. Com relação à microestrutura, o aditivo SCA diminuiu o grau de hidratação e aumentou a porosidade total, com o aumento da proporção do volume de macroporos. / The aim of this research was the study of the influence of shrinkage reducing admixture (SRA) and shrinkage compensating admixture (SCA) in mortars and pastes of blast furnace slag activated with sodium silicate. The method was centered in the analysis of free drying and autogenous shrinkage, with other characteristics that affect the shrinkage, as the mechanical properties. The microstructure behavior was accomplished with thermogravimetry (TG), mercury intrusion porosimetry (MIP) and X-ray diffraction (XRD). The samples were prepared with 0,5%, 1%, 1,5% and 2% of SRA admixture and 5%, 10% and 15% of SCA admixture, by binder mass. The effect of water/binder ratio was accomplished in three contents: 0,40, 0,48 and 0,56. In the reference mixtures, without admixtures, it was observed that an increase of water/binder ratio incurs in an increase of drying and autogenous shrinkage of alkali activated slag. The explanations for drying shrinkage behavior are the decrease of mechanical strength as consequence of water/binder increase, that turns the porous structure more susceptible to deformations, and the increase of the capillary tensions, attributed to the increase of free water to be evaporated. The increase of autogenous shrinkage with water/binder ratio is attributed to the increase of pore volume with diameter in the mesopores range, besides the decrease of the mechanical strength. The shrinkage reducing admixture (SRA) diminish drying shrinkage of 40% up to 74% at 28 days, however, this type of admixture was not capable to combat the autogenous shrinkage. About mechanical strength, the SRA admixture incurs in a decrease up to 40% of compression strength that it was attributed to the decrease of the hydration degree and retard of pore size refinement. The shrinkage compensating admixture (SCA) softened drying and autogenous shrinkage, reducing in up to 64% and 70%, respectively. However, the SCA admixture decreases in up to 60% mechanical strength of alkali activated slag. About microstructure, SCA admixture reduced the hydration degree and it increased the total porosity, with the increase of macropores volume.

The electrical resistivity is an important concrete property that allows evaluating the access facility of aggressive agents before the corrosion process begins and estimates the velocity of the same process after it begun. The electrical resistivity and the oxygen availability are the characteristics that control the corrosion velocity. This work aimed to evaluate the performance of white Portland cement concretes with high blast furnace slag content and chemical activation on the electrical resistivity. Other properties were measured, as axial compressive strength, porosity and specific electrical conductivity of pore solution. Four mixtures were tested, a reference one, only with white Portland cement as binder, a second one, with 50% of blast furnace slag in substitution of cement, other with 70% slag content, and the last one, with 50% of slag and alkaline activation, 4% of Na2SO4. The water/binder ratios were fixed at 0,30, 0,42 and 0,55 for all samples. The electrical resistivity was measured using the four electrode method (Wenner method). The sample age, water/binder ratio and the slag content have an expressive effect over the electrical resistivity, especially because it results in changes of the pore structure. The electrical resistivity grows as the amount of slag increases. The increase of slag amount also results in smaller specific electrical conductivity of pore solution and pore structure refinement. On the other hand, the axial compressive strength decreases as the slag amount increases. The biggest resistivity results were obtained for the mixture with 70% of slag. This mixture showed the best cost/benefit ratio as compressive strength were fixed at 35 and 55 MPa, at 28 days, and 60 MPa, at 91 days. / A resistividade elétrica é uma importante propriedade do concreto por permitir avaliar a facilidade de acesso de agentes agressivos antes de instalado o processo corrosivo e estimar a velocidade do mesmo depois de instalado, sendo conjuntamente com a disponibilidade de oxigênio um dos parâmetros determinantes para a velocidade da corrosão. Este trabalho teve como objetivo avaliar o desempenho de concretos de cimento Portland branco com elevados teores de escória de alto forno e ativação química quanto à resistividade elétrica aparente. Foram avaliadas além da resistividade outras grandezas como resistência à compressão, porosidade e condutividade específica da solução dos poros. Foram investigadas quatro misturas, uma de referência contendo apenas cimento, uma segunda com teor de substituição de cimento por escória de 50%, outra com teor de substituição de 70% e uma última contendo 50% de escória e ativador alcalino, Na2SO4, em um teor de 4%. As relações água/aglomerante foram fixadas em 0,30, 0,42 e 0,55 para todas as misturas. A medida da resistividade elétrica foi realizada através do método dos quatro eletrodos (Wenner). A resistividade elétrica se mostrou dependente da idade, relação a/ag e teor de escória, principalmente, em função das alterações que estas proporcionam na estrutura de poros da pasta. A resistividade cresceu proporcionalmente ao aumento do teor de escória. O aumento do teor de escória resultou também em menor condutividade da solução aquosa e refinamento da estrutura de poros da pasta. Por outro lado, a resistência à compressão diminuiu com o crescimento do teor de escória. Os maiores valores de resistividade elétrica foram apresentados pela mistura contendo 70% de escória. Esta mistura se mostrou a de melhor relação custo/benefício quando se fixaram valores de resistência à compressão de 35 e 55 MPa, aos 28 dias, e 60 MPa, aos 91 dias.

Abstract The blast furnace – basic oxygen furnace route remains the most utilised process route in the production of steel worldwide. Coke is the main fuel of the blast furnace process, however, coke producers and blast furnace operators are facing significant challenges due to increased demands on coke quality and decrease of prime coking coals. The estimation of coke performance in the industrial process through accurate laboratory analyses is of increasing importance. In this doctoral thesis, the aim was to study phenomena related to coke properties and its analysis methods in blast furnace simulating conditions. A new method was introduced to measure the hot strength of coke using a Gleeble 3800 thermomechanical simulator. The hot strengths of industrial cokes were determined at various temperatures and several coke properties, which were believed to affect hot strength, were determined. The effect of H₂ and H₂O in the blast furnace shaft gas were determined in relation to coke reactivity, threshold temperature, and the gasification mechanism. The results obtained by this thesis show that the Gleeble device is suitable for study of coke hot strength. The coke strength was significantly decreased for all three coke grades at temperatures of 1600 °C and 1750 °C when compared to room temperature or 1000 °C. The deformation behaviour of coke was fragile up to 1000 °C, but became at least partially plastic at 1600 °C, and the plasticity further increased at 1750 °C. Notable changes were observed in the deformation behaviour between coke grades at high temperatures. The presence of H₂ and H₂O in the BF shaft gas strongly increased coke reactivity and changed the reaction mechanism of coke to be more surface centric in a specific temperature range. The reactivity of coke in the conditions 100 vol-% CO₂ did not directly correlate with reactivity in a simulated blast furnace shaft gas, which suggest that the widely utilised CRI test does not accurately estimate coke reactivity in the industrial blast furnace process. / Tiivistelmä Masuuni – konvertteri yhdistelmä on edelleen käytetyin prosessireitti teräksen tuotantoon ympäri maailman. Koksi on masuunin tärkein polttoaine. Koksintuottajat ja masuunioperaattorit ovat suurten haasteiden edessä johtuen koksin kasvaneista laatuvaatimuksista ja parhaiden koksautuvien kivihiilten ehtymisestä. Koksin suoriutumisen arviointi masuunin olosuhteissa tarkoilla laboratorioanalyyseillä on yhä merkittävämmässä roolissa. Tässä väitöskirjassa tavoitteena oli tuottaa uutta tietoa koksin ominaisuuksista ja sen analyysimenetelmistä simuloiduissa masuunin olosuhteissa. Uusi metodi esitettiin koksin kuumalujuuden määrittämiseksi Gleeble 3800 termomekaanisella simulaattorilla. Teollisten koksilaatujen kuumalujuuksia määritettiin eri lämpötiloissa ja useita koksin mitattiin, joilla uskottiin olevan vaikutus kuumalujuuteen. Lisäksi työssä tutkittiin masuunin kuilun kaasuatmosfäärissä H2 ja H2O kaasujen vaikutusta koksin kemialliseen reaktiivisuuteen, kaasuuntumisen kynnyslämpötilaan ja reaktiomekanismiin. Tässä työssä esitetyt tulokset osoittavat että Gleeble soveltuu koksin kuumalujuuden määritykseen. Koksin lujuus aleni merkittävästi kaikilla kolmella koksilaadulla kuumennettaessa 1600 ja 1750 °C lämpötiloihin verrattuna huoneenlämpötilaan tai 1000 °C lämpötilaan. Koksin muodonmuutos oli haurasta aina 1000 °C lämpötilassa, mutta muuttui osittain plastiseksi 1600 °C lämpötilassa ja plastisuus kasvoi kun lämpötilaa nostettiin 1750 °C:een. Huomattavia eroja havaittiin eri koksilaatujen muodonmuutoskäyttäytymisessä korkeissa lämpötiloissa. H₂ ja H₂O kaasujen läsnäolo kuilun kaasuatmosfäärissä kasvatti voimakkaasti koksin reaktiivisuutta ja muutti kaasuuntumismekanismia pintakeskisemmäksi rajatulla lämpötila-alueella. Koksin reaktiivisuus 100 % CO₂ kaasussa ei korreloinut suoraan simuloidun masuunin kuilun kaasuatmosfäärin kanssa. Tämä tulos indikoi sitä että maailmalla yleisesti käytetty CRI testi ei ennusta tarkasti koksin reaktiivisuutta masuunissa.

Abstract Most of the iron in the world is produced using a blast furnace process, which has iron ore (iron oxides) and coke as its raw materials. When pellets are used in a blast furnace, the iron burden material is charged in the form of pellets and fine, iron-rich by-products are charged typically in the form of cold-bonded briquettes at the top of the blast furnace. Coke is the primary fuel and reductant in the blast furnace. Coke reacts with the oxygen of the blast air and forms carbon monoxide in the up-flowing gas, which reduces the descending iron oxide burden. In addition, carbon and hydrogen bearing reductants are injected from the tuyeres in the lower part of the furnace. Hydrogen partially replaces the carbon monoxide as a reducing agent and changes the composition of the reducing gas. The high temperature properties of the burden have a significant effect on the flow of reducing gas and formation of the cohesive zone which markedly affect the furnace efficiency. The raw materials are commonly stored outdoors and therefore include moisture in varying amounts. In addition, the briquette contains chemically bound water. The rate of injected reductants, the high temperature properties and the water content of the raw materials have significant effects on blast furnace performance. They cause various phenomena in the blast furnace which set limitations on the process. The limiting phenomena related to the use of pellets in the blast furnace were studied in this doctoral thesis with the aim of obtaining additional knowledge about the limiting phenomena. The results show that hydrogen increases the reduction rate of iron oxides at temperatures below 850 °C. High water vapour concentration causes a rapid conversion through a catalysed water-gas shift reaction at above 300 °C in a gas mixture similar to the one in the upper part of the blast furnace. The reduction rate of the cold-bonded briquette is higher than pellets due to a self-reducing effect. The phase transformations occurring in the briquette during reduction follow the path of phase equilibria. The softening of the pellet is caused by the formation of melt which initiates wüstite dissolution in the surrounding slag phase. / Tiivistelmä Suurin osa maailmassa valmistettavasta raudasta tuotetaan masuuniprosessilla, jonka pääraaka-aineita ovat rautarikaste eli raudan oksidit ja koksi. Masuunissa, jossa käytetään pellettiä, rautarikaste panostetaan pelletin muodossa ja hienojakeiset rautapitoiset sivutuotteet tyypillisesti kylmäsidottuna brikettinä masuunin huipulta. Koksi on masuunin pääasiallinen polttoaine ja pelkistin, joka masuunin sisään puhallettavan ilman hapen kanssa reagoidessaan muodostaa ylöspäin virtaavaan kaasuun hiilimonoksidia, joka pelkistää masuunin kuilussa vajoavat rautaoksidit. Lisäksi yleensä käytetään hiiltä ja vetyä sisältäviä pelkistysaineita, jotka injektoidaan masuuniin alaosan hormeilta. Vety korvaa osittain hiilimonoksidia rautaoksidien pelkistimenä ja muuttaa pelkistävän kaasun koostumusta. Panosmateriaalien korkealämpötilaominaisuudet vaikuttavat suuresti kuilun kaasuvirtauksiin ja koheesiovyöhykkeen muodostumiseen masuunissa, mitkä vaikuttavat merkittävästi masuunin tehokkuuteen. Suurista määristä johtuen raaka-aineet varastoidaan usein ulkona, joten ne sisältävät kosteutta vaihtelevissa määrin. Lisäksi briketti sisältää kemiallisesti sitoutunutta vettä. Injektoitavien pelkistysaineiden käyttömäärällä, raaka-aineiden korkealämpötilaominaisuuksilla ja vesipitoisuudella on merkittäviä vaikutuksia masuunin toimintaan. Ne aikaansaavat masuunissa erilaisia ilmiöitä, jotka asettavat prosessille rajoituksia. Tässä väitöskirjassa tutkittiin näitä masuunille rajoituksia asettavia ilmiöitä ja pyrittiin lisäämään tietämystä niistä. Tulokset osoittavat, että vety nopeuttaa rautaoksidien pelkistymistä alle 850 °C lämpötilassa. Suuri vesihöyrymäärä johtaa nopeaan konversioon masuunin yläkuilun aluetta vastaavassa kaasuseoksessa yli 300 °C lämpötilassa katalysoidun vesikaasun siirtoreaktion kautta. Kylmäsidottu briketti pelkistyy pellettiä nopeammin itsepelkistymisen vaikutuksesta. Briketin pelkistyessään läpikäymät faasitransformaatiot seuraavat faasien tasapainotiloja. Pelletin pehmenemisen aiheuttaa sulan muodostuminen, joka laukaisee wüstiitin liukenemisen sitä ympäröivään sulaan kuonafaasiin.

Abstract A blast furnace is the dominant process for making iron in the world. Iron ore pellets are commonly used as iron burden materials in a blast furnace, in which iron oxides are reduced to metallic molten iron. While descending, the charge faces various stresses, which affect the gas flows in the shaft and the energy efficiency of the process. Charge material testing on a laboratory scale is of crucial importance in regard to the development of material quality. This doctoral thesis presents a couple of advanced novel experimental methods: a novel camera imaging method to determine the amount of swelling during reduction; a novel reducibility test to determine the reducibility in a solid state under simulated blast furnace conditions; and a novel experimental program for the ARUL reduction-softening test to more accurately simulate blast furnace conditions. Swelling tests under conditions of fixed temperature and gas composition showed that isothermal tests do not give a realistic insight into the material behaviour in a blast furnace. As a result, it is suggested that dynamic gas composition – temperature programmes simulating actual process conditions should be used. Additionally, the test results showed that circulating elements (sulphur and potassium) also affect the pellet volume change during reduction, however no abnormal swelling was observed in any of the swelling experiments. The factors affecting the high-temperature properties of iron burden materials for blast furnace use were evaluated by both the experimental methods and computational thermodynamics. It was shown that none of the studied pellet grades has as good reduction-softening properties as the fluxed sinter because of the differences in the chemistry and macro-porosity. FeO-SiO2-CaO-MgO-Al2O3 system examinations with FactSage was found to be a useful tool for predicting the softening of an iron burden material using the original chemical composition. FactSage computations suggest that the softening properties of an iron burden material can be improved either by decreasing the proportion of SiO2, increasing the proportion of MgO or introducing an appropriate amount of CaO in relation to the proportion of SiO2. / Tiivistelmä Masuuni on merkittävin raakaraudan valmistusprosessi maailmassa. Masuunissa käytetään yleisesti rautamalmipellettejä rautapanosmateriaalina. Masuunissa raudanoksidit pelkistetään metalliseksi rautasulaksi. Vajotessaan panos kohtaa monenlaisia rasitteita, joilla on vaikutusta kuilun kaasuvirtauksiin ja masuuniprosessin energiatehokkuuteen. Panosmateriaalien testaus laboratoriomittakaavassa on merkittävässä roolissa, kun niiden laatua kehitetään. Väitöskirjassa esitetään useita kehittyneitä koemenetelmiä: uusi kamerakuvausmenetelmä, jolla voidaan määrittää turpoaminen pelkistyksen edetessä; uusi pelkistyvyystesti, jolla voidaan määrittää rautapanosmateriaalin pelkistyminen kiinteässä tilassa masuunia jäljittelevissä olosuhteissa; ja uusi koeohjelma, jolla voidaan jäljitellä aiempaa tarkemmin masuuniolosuhteita sulamis-pehmenemiskokeessa. Turpoamistestit vakioiduissa olosuhteissa osoittivat, että isotermiset testit eivät anna realistista kuvaa materiaalin käyttäytymisestä masuunissa. Tämän vuoksi dynaamisia kaasukoostumus–lämpötila-ohjelmia tulisi suosia. Lisäksi tutkimustulokset osoittavat, että myös masuunissa kiertävillä komponenteilla (rikillä ja kaliumilla) on vaikutusta pelletin tilavuuden muutokseen pelkistyksessä. Yhdessäkään turpoamiskokeessa ei kuitenkaan havaittu katastrofaalista turpoamista. Masuunin rautapanosmateriaalien korkealämpötilaominaisuuksiin vaikuttavia tekijöitä arvioitiin sekä kokeellisin menetelmin että termodynaamisin laskelmin. Yhdelläkään tutkitulla pellettilaadulla ei havaittu sintterin veroisia korkealämpötilaominaisuuksia, mikä johtuu eroista kemiallisessa koostumuksessa ja makrohuokoisuudessa. FeO-SiO2-CaO-MgO-Al2O3 systeemitarkastelut rautapanosmateriaalin lähtökoostumuksella todettiin toimivaksi menetelmäksi arvioida panosmateriaalin pehmenemiskäyttäytymistä. FactSage-laskennat antavat ymmärtää, että rautapanosmateriaalin pehmenemisominaisuuksia voidaan parantaa joko vähentämällä SiO2:n osuutta, lisäämällä MgO:n osuutta tai lisäämällä CaO:ta sopiva määrä SiO2:n osuuteen nähden.

Fossil fuel reserves are projected to be decreasing, and emission regulations are becoming more stringent due to increasing atmospheric pollution. Alternative fuels for power generation in industrial gas turbines are thus required able to meet the above demands. Examples of such fuels are synthetic gas, blast furnace gas and coke oven gas. A common characteristic of these fuels is that they are multi-component fuels, whose composition varies greatly depending on their production process. This implies that their combustion characteristics will also vary significantly. Thus, accurate and yet flexible enough combustion sub-models are required for such fuels, which are used during the design stage, to ensure optimum performance during practical operating conditions. Most combustion sub-model development and validation is based on Direct Numerical Simulation (DNS) studies. DNS however is computationally expensive. This, has so far limited DNS to single-component fuels such as methane and hydrogen. Furthermore, the majority of DNS conducted to date used one-step chemistry in 3D, and skeletal chemistry in 2D only. The need for 3D DNS using skeletal chemistry is thus apparent. In this study, an accurate reduced chemical mechanism suitable for multi-component fuel-air combustion is developed from a skeletal mechanism. Three-dimensional DNS of a freely propagating turbulent premixed flame is then conducted using both mechanisms to shed some light into the flame structure and turbulence-scalar interaction of such multi-component fuel flames. It is found that for the multi-component fuel flame heat is released over a wider temperature range contrary to a methane flame. This, results from the presence of individual species reactions zones which do not all overlap. The performance of the reduced mechanism is also validated using the DNS data. Results suggest it to be a good substitute of the skeletal mechanism, resulting in significant time and memory savings. The flame markers commonly used to visualize heat release rate in laser diagnostics are found to be inadequate for the multi-component fuel flame, and alternative markers are proposed. Finally, some popular mean reaction rate closures are tested for the multi-component fuel flame. Significant differences are observed between the models’ performance at the highest turbulence level considered in this study. These arise from the chemical complexity of the fuel, and further parametric studies using skeletal chemistry DNS would be useful for the refinement of the models.

Alkali activated materials (AAMs) represent construction materials with a huge potential especially because of environmental and economic aspects but sufficient mechanical properties as well. A fibre or fabric reinforcement of the AAMs could support more widespread application potential due to the mechanical properties, fracture toughness or composite durability improvement. Various alkaline activators were used for a blast furnace slag (BFS) activation to produce a suitable matrix for basalt fibres (BF) implementation in this thesis. The BFs represent applicable reinforcing material because of its favourable mechanical and thermal properties. Still, the utilization of BFs in the AAMs is quite limited due to the fibres low chemical stability under the alkaline conditions. Accelerated leaching tests with a determination of basalt fibres chemical composition same as tensile strength change using various analytical techniques (XRD, XPS, SEM-EDX, ICP-OES) have confirmed these assumptions. An influence of basalt fabric reinforcement in one or more layers on the mechanical properties was determined with the meaning of the compressive and flexural strengths. The fibre/matrix adhesion and transition zone properties were studied using SEM-EDX and pull-out tests as well because they are crucial parameters for the composite material reinforcement efficiency.