Os componentes automotivos em geral devem atender a especificações rigorosas de propriedades mecânicas, requisitos de limpeza inclusionária, entre outros. Enxofre e alumínio são elementos adicionados ao banho líquido de aço que desempenham um papel importante na obtenção destas propriedades. Porém, eles que dificultam o processo de produção por lingotamento contínuo por favorecerem a formação de partículas sólidas de alto ponto de fusão, que podem causar a obstrução das válvulas de lingotamento e dificultar o processo de desenvolvimento de aços com alta limpeza inclusionária. O objetivo do presente trabalho foi estudar a composição química do aço DIN 38MnSiVS6, focando nos elementos químicos que afetam a formação e remoção de inclusões, assim como a composição química da escória e outros parâmetros da aciaria como a temperatura e a lingotabilidade do processo de produção em escala industrial. Neste estudo, foi avaliada a hipótese de melhoria da lingotabilidade e da limpeza do aço através da alteração da etapa de adição de enxofre e também da quantidade de adição de cálcio Amostras de aço retiradas ao longo do processo foram analisadas através de microscopia ótica e eletrônica de varredura e também por ultrassom por imersão. Os dados de composição química foram sobrepostos a janelas de lingotabilidade e as características das escórias foram avaliadas por simulação termodinâmica. Foram avaliadas as correlações entre os resultados das diferentes técnicas de análise e com as referências de literatura. A hipótese de redução da quantidade de cálcio se mostrou satisfatória tanto para a melhoria da lingotabilidade quanto para a limpeza do aço. Porém, a alteração da etapa de adição de enxofre necessita de mais testes para comprovar sua eficiência. Dentre as técnicas empregadas, o uso do microscópio eletrônico de varredura acoplado a um sistema automatizado de análise de inclusões (ASPEX) se mostrou como uma ferramenta vantajosa por fornecer uma ampla gama de informações que podem auxiliar no entendimento da lingotabilidade e da limpeza inclusionária do aço. / Automotive components in general must meet stringent specifications of mechanical properties, inclusionary cleanliness requirements, among others. Sulfur and aluminum are elements added to the liquid steel bath which play an important role in obtaining these properties, but which hinder the production process by continuous casting by favoring the formation of solid particles of high melting point, that can cause the nozzle clogging and hamper the development process of steels with high inclusionary cleanliness. The aim of the present work is to study the chemical composition of the DIN 38MnSiVS6 steel, focusing on the chemical elements that affect the formation and removal of inclusions, as well as the chemical composition of the slag and other parameters such as temperature and castability in an industrial scale production process. In this study, the hypothesis steel cleanliness improvement was evaluated by changing the stage of sulfur addition as well as the amount of calcium addition. Steel samples collected throughout the process were analyzed by optical and scanning electron microscopy, and by immersion ultrasound. The chemical composition data were superimposed on liquid windows and the slag characteristics were evaluated by thermodynamic simulation. The correlations between the results of the different analysis techniques and the literature references were evaluated. The hypothesis of reduction in the amount of calcium was satisfactory both for the improvement of the castability and for the cleanliness of the steel, but the change of the sulfur addition stage requires more tests to prove its efficiency. The scanning electron microscope coupled with an automated inclusion analysis system (ASPEX) has proved to be an advantageous tool to provide a wide range of information that can help in the understanding of the castability and cleanliness of steel.

Há uma demanda por competitividade entre as indústrias de aços, a fim de alcançar a excelência definida pelo termo clean steel. O processo de desgaseificação a vácuo (VD) ocorre durante o Refino Secundário de aços especiais. Sua principal função é remover gases indesejáveis, especialmente o hidrogênio. Entretanto, durante este processo, o fenômeno de flotação e a absorção de inclusões são reportados. O objetivo do presente trabalho foi estudar a viscosidade de escórias e a capacidade da estação de desgaseificação a vácuo do tipo tanque na limpeza de aços sob uma perspectiva industrial. Para realizar este objetivo, foram coletadas amostras de escória e aço antes e após a etapa de vácuo. Os resultados em limpeza de aço foram relacionados à energia de agitação durante o tratamento a vácuo (associada a um parâmetro cinético - βs) e ao efeito da viscosidade de escórias. É possível observar um decréscimo expressivo na população de inclusões entre as condições antes e após tratamento de desgaseificação a vácuo. A remoção de inclusões durante o vácuo atinge 64, 75 e 78% para as faixas de diâmetro de 2,5-5, 5-15 e ≥ 15 μm, respectivamente. Após o processo de desgaseificação, a composição das inclusões não-metálicas aproxima-se da composição química da escória. O processo de agitação na estação de desgaseificação a vácuo promove uma diminuição significativa na densidade de inclusões na faixa de diâmetro de 2,5-15 μm. Além disso, ao aumentar a intensidade do parâmetro cinético, a composição química de inclusões não-metálicas foi afetada e o teor de enxofre presente no aço líquido foi reduzido. Quanto às viscosidades efetiva das escórias, conclui-se que, para valores mais baixos (0,20 Pa.s) aumenta-se a capacidade da escória na remoção de inclusões, enquanto que valores mais altos (> 0,40 Pa.s) aparentaram ser prejudiciais à limpeza do aço. / There is a demand in competitiveness within the steel industry towards achieving excellence defined by clean steel term. The process of vacuum degassing (VD) occurs during the secondary refining of special steels. Its main function is to remove undesirable gases, primarily hydrogen. However, during this process, flotation phenomenon and inclusions absorption are reported. The aim of the present work was to study the slag viscosity and vacuum degassing (tank type) capacity in steel cleanliness from an industry perspective. To achieve this objective, slag and steel samples were taken before and after vacuum stage. The results in steel cleanliness were related to the stirring energy of the vacuum station (associated to a kinetic parameter – βs) and to the effect of slag viscosity. It is possible to observe an expressive decrease in the population of inclusions between the conditions before and after vacuum degassing treatment. The removal of inclusions during the vacuum stage reaches 64, 75 and 78% in the diameter ranges of 2,5-5, 5-15 and ≥ 15 μm, respectively. After the degassing process, the composition of non-metallic inclusions seemed to approach the slags’ chemical compositions. The stirring process in the vacuum degassing station promotes a significant decrease in the inclusion density with 2,5-15 μm diameter range. Also, by increasing the kinetic parameter intensity, the composition of non-metallic inclusions was affected. The sulfur content present in liquid steel was reduced. Regarding the effective viscosities of slags, it was concluded that lower values (0,20 Pa.s) increased slag capacity in inclusion removal, whereas higher values (> 0,40 Pa.s) was detrimental to steel cleanliness.

No description available.

Sulfide Stress Cracking (SSC) resistance of the newly developed API-X100 High Strength Low Alloy (HSLA) steel was investigated in the NACE TM0177 "A" solution. The NACE TM0177 "A" solution is a hydrogen sulfide (H2S) saturated solution containing 5.0 wt.% sodium chloride (NaC1) and 0.5 wt.% acetic acid (CH3COOH). The aim of this thesis was to study the effect of microstructure, non-metallic inclusions and alloying elements of the X100 on H2S corrosion and SSC susceptibility. The study was conducted by means of electrochemical polarization techniques and constant load (proof ring) testing. Microstructural analysis and electrochemical polarization results for X100were compared with those for X80, an older generation HSLA steel. Uniaxial constant load SSC testing was conducted using X100 samples and the results were compared with those reported for older generation HSLA steels. Addition of H2S to the NACE TM0177 "A" solution increased the corrosion rate of X100from 51.6 to 96.7 mpy. The effect of H2S on the corrosion rate was similar for X80. The corrosion rate for X80 increased from 45.2 to 80.2 mpy when H2S was added to the test solution. Addition of H2S enhanced the anodic kinetics by forming a catalyst (FeHSads) on the metal surface and as a result, shifted the anodic polarization curve to more current densities. Moreover, the cathodic half cell potential increased due to the decrease in pH, from 2.9 to 2.7, which shifted the cathodic polarization curve to more current densities. The increase in both the anodic and cathodic currents, after H2S addition, caused the rise in the corrosion current density. In H2S saturated NACE TM-0177 "A" solution, the X100 steel corrosion rate was higher than the X80 steel by 20%. Longer phase boundaries and larger nonmetallic inclusions in the X100 microstructure generated more areas with dissimilar corrosion potentials and therefore, a stronger driving force for corrosion. Higher density of second phase regions and larger nonmetallic inclusions acted as an increased cathode area on the X100 surface which increased the cathodic current density and consequently, increased the corrosion current density. Proof ring tests on the X100 gave a threshold stress value, C5th, of 46% YS, 343.1 MPa(49.7 ksi). The main failure was caused by SSC cracking. SSC nucleated at corrosion pits on the metal surface and microcracks in the metal body and propagated perpendicular to the applied stress. Hydrogen Induced Cracking (HIC) was observed in the X100. HIC cracks nucleated at banded martensite-ferrite interfaces and propagated along the rolling direction parallel to the applied tensile stress through the softer ferrite phase. When compared to older HSLA grades, the X100 tested in this study had a high SSC susceptibility and therefore, is not be recommended for H2S service applications. The high X100 SSC susceptibility was caused by the material high corrosion rates in H2Smedia which formed corrosion pits that acted as crack initiation sites on the metal surface and provided more hydrogen that migrated into the steel. In addition, the X100 inhomogeneous microstructure provided a high density of hydrogen traps in front of the main crack tip which promoted SSC microcrack formation inside the metal. Microcracks in the metal body connected with the main crack tip that originated from corrosion pits which assisted SSC propagation.

No description available.

Sulfide Stress Cracking (SSC) resistance of the newly developed API-X100 High Strength Low Alloy (HSLA) steel was investigated in the NACE TM0177 "A" solution. The NACE TM0177 "A" solution is a hydrogen sulfide (H2S) saturated solution containing 5.0 wt.% sodium chloride (NaC1) and 0.5 wt.% acetic acid (CH3COOH). The aim of this thesis was to study the effect of microstructure, non-metallic inclusions and alloying elements of the X100 on H2S corrosion and SSC susceptibility. The study was conducted by means of electrochemical polarization techniques and constant load (proof ring) testing. Microstructural analysis and electrochemical polarization results for X100were compared with those for X80, an older generation HSLA steel. Uniaxial constant load SSC testing was conducted using X100 samples and the results were compared with those reported for older generation HSLA steels. Addition of H2S to the NACE TM0177 "A" solution increased the corrosion rate of X100from 51.6 to 96.7 mpy. The effect of H2S on the corrosion rate was similar for X80. The corrosion rate for X80 increased from 45.2 to 80.2 mpy when H2S was added to the test solution. Addition of H2S enhanced the anodic kinetics by forming a catalyst (FeHSads) on the metal surface and as a result, shifted the anodic polarization curve to more current densities. Moreover, the cathodic half cell potential increased due to the decrease in pH, from 2.9 to 2.7, which shifted the cathodic polarization curve to more current densities. The increase in both the anodic and cathodic currents, after H2S addition, caused the rise in the corrosion current density. In H2S saturated NACE TM-0177 "A" solution, the X100 steel corrosion rate was higher than the X80 steel by 20%. Longer phase boundaries and larger nonmetallic inclusions in the X100 microstructure generated more areas with dissimilar corrosion potentials and therefore, a stronger driving force for corrosion. Higher density of second phase regions and larger nonmetallic inclusions acted as an increased cathode area on the X100 surface which increased the cathodic current density and consequently, increased the corrosion current density. Proof ring tests on the X100 gave a threshold stress value, C5th, of 46% YS, 343.1 MPa(49.7 ksi). The main failure was caused by SSC cracking. SSC nucleated at corrosion pits on the metal surface and microcracks in the metal body and propagated perpendicular to the applied stress. Hydrogen Induced Cracking (HIC) was observed in the X100. HIC cracks nucleated at banded martensite-ferrite interfaces and propagated along the rolling direction parallel to the applied tensile stress through the softer ferrite phase. When compared to older HSLA grades, the X100 tested in this study had a high SSC susceptibility and therefore, is not be recommended for H2S service applications. The high X100 SSC susceptibility was caused by the material high corrosion rates in H2Smedia which formed corrosion pits that acted as crack initiation sites on the metal surface and provided more hydrogen that migrated into the steel. In addition, the X100 inhomogeneous microstructure provided a high density of hydrogen traps in front of the main crack tip which promoted SSC microcrack formation inside the metal. Microcracks in the metal body connected with the main crack tip that originated from corrosion pits which assisted SSC propagation.

The presence of different types of defects is an important reality for manufacturers and users of engineering materials. Generally, the defects are either considered to be the unwanted products of impurities in the raw materials or to have been introduced during the manufacturing process. In high-quality steel materials, such as tool steel, the defects are usually non-metallic inclusions such as oxides or sulfides. Traditional methods for purity control during standard manufacturing practice are usually based on the light optical microscopy scanning of polished surfaces and some statistical evaluation of the results. Yet, as the steel manufacturing process has improved, large defects have become increasingly rare. A major disadvantage of the traditional quality control methods is that the accuracy decreases proportionally to the increased rarity of the largest defects unless large areas are examined. However, the use of very high cycle fatigue to 109 cycles has been shown to be a powerful method to locate the largest defects in steel samples. The distribution of the located defects may then be modelled using extreme value statistics. This work presents new methods for determining the volume distribution of large defects in high-quality steels, based on ultrasonic fatigue and the Generalized Extreme Value (GEV) distribution. The methods have been developed and verified by extensive experimental testing, including over 400 fatigue test specimens. Further, a method for reducing the distributions into one single ranking variable has been proposed, as well as a way to estimate an ideal endurance strength at different life lengths using the observed defects and endurance limits. The methods can not only be used to discriminate between different materials made by different process routes, but also to differentiate between different batches of the same material. It is also shown that all modes of the GEV are to be found in different steel materials, thereby challenging a common assumption that the Gumbel distribution, a special case of the GEV, is the appropriate distribution choice when determining the distribution of defects. The new methods have been compared to traditional quality control methods used in common practice (surface scanning using LOM/SEM and ultrasound C-scan), and suggest a greater number of large defects present in the steel than could otherwise be detected.

A limpeza dos aços está diretamente associada ao conteúdo de óxidos dos mesmos, sendo que os diferentes tipos de inclusões não-metálicas presentes podem prejudicar desde os processos de fabricação e conformação até as características necessárias para a aplicação do produto final. As inclusões se formam e se modificam ao longo dos processos de fabricação, e estão relacionadas principalmente às práticas de refino secundário e de lingotamento. Essas inclusões estão sempre presentes nos aços, de modo que é impossível se produzir um aço completamente livre das mesmas. Atualmente, existe uma série de pesquisas buscando o desenvolvimento de práticas e de processos para incrementar a limpeza dos aços. Entre essas está o desenvolvimento de novos materiais refratários adequados às diversas etapas de uma Aciaria. Com especial importância na limpeza dos aços estão as práticas e tecnologias aplicadas no lingotamento contínuo. Neste trabalho foi avaliada a influência do uso de nitrogênio injetado através de poros no colo das válvulas submersas sobre a lingotabilidade e limpeza dos produtos laminados a partir de tarugos. Para este estudo foram testadas diferentes vazões de gás e depois mensurado seu efeito. As técnicas utilizadas para a avaliação foram: verificação da abertura dos tampões; índice de sucateamento nas linhas de inspeção; severidade em ultrassom pelo método de imersão; análise dos teores de oxigênio total e nitrogênio e análise pelo método de distribuição de valores extremos da maior inclusão estimada. Os resultados práticos foram então comparados entre os lotes escolhidos para o teste. Verificou-se através dos dados coletados boa compatibilidade entre as diferentes variáveis e coerência dos resultados com os relatos da literatura. O uso de gás nitrogênio se mostrou ser potencialmente benéfico para a melhoria da limpeza e lingotabilidade do aço, apesar de mais testes serem necessários para a validação das hipóteses levantadas. / The steel cleanliness is directly associated to its inclusion content. The different kind of non-metallic inclusion can harm from the manufacturing and forming processes up to the demanding characteristics for the final products. The inclusions are formed and modified along the steel manufacturing process, and they are related mainly to the secondary refining and casting of steel. These inclusions are always present in the steel, so it is hardly possible to produce steels completely free of them. Nowadays, there are several fields of research concerning with the development of practices and processes to improve steel cleanliness. The development of new lining materials which are suitable for each melting shop step is one of these fields. With special importance over the steel cleanliness issue, the practices and technologies applied to the continuous casting process can be cited. In this work, the influence of nitrogen injection though the pores of the submerged entry nozzle over the castability and cleanliness of rolled products was evaluated. For this study, different gas flows were tested and then measured its effects. The techniques used for the evaluation were: stopper rod opening; rejection index during the inspection lines; severity in immersion ultra-sonic inspection; total oxygen and nitrogen content analysis and largest inclusion diameter estimated by extreme values distribution. The practical results for each lot of steel were then compared. It was verified from, the collected data, good compatibility between these different variables and coherency of the results with the experiences reported in the literature. The use of nitrogen gas showed itself to be potentially good for the improvement of cleanliness and castability of steel, though more trials are necessary for the validation of the considered hypothesis.

Abstract Non-metallic inclusions are unavoidable particles in steel and are often detrimental to the steelmaking process and the mechanical properties of the steel. While it is not feasible to remove all inclusions, in the well-established calcium treatment of aluminium-killed steel, solid aluminium oxides are transformed into less harmful liquid calcium aluminates. The main objective of this work was to develop a new inclusion identification and classification method. The presented method offers valuable information on phases of the inclusions. This data is often buried within simple inclusion classification criteria. The method offers the best approximation of the phases in each inclusion detected with minimal time, if no time-consuming elemental map analyses are available. In this work, applications for the inclusion phase identification method are presented. Utilising the method, the dispersion and evolution of inclusions during the sampling of liquid steel in lollipop samples is investigated, as well as the evolution of inclusions during continuous casting. New information is obtained on the elongation of inclusions and formation of oxide–sulphide stringers during hot rolling. The results for the investigated steels show that with sulphur contents higher than 10 ppm, calcium aluminates were back-modified to alumina and spinel inclusions during casting. However, with decreasing sulphur contents, and adequate simultaneous calcium treatment of oxides, Al₂O₃ and spinel formation is hindered or even avoided. The most elongated inclusions are often also found in stringers. According to the results of this study, low melting calcium aluminate inclusions are not the most elongated oxide inclusions in the hot rolled product. With moderate calcium treatment, an optimal oxide composition can be obtained, found within the C12A7–CA–MgO composition. These liquid inclusions ensure good castability, while they do not easily elongate or fragment into detrimental stringers after continuous casting. / Tiivistelmä Epämetalliset sulkeumat ovat väistämättä osa terästä, ja ne aiheuttavat ongelmia prosessille ja teräksen mekaanisille ominaisuuksille. Sulkeumien poiston sijaan niiden koostumusta muokataan kalsiumkäsittelyllä. Tällöin kiinteät alumiinioksidit muuttuvat vähemmän ongelmallisiksi suliksi kalsiumaluminaateiksi. Tämän työn päätavoitteena oli kehittää uusi sulkeumien tunnistus- ja luokittelumenetelmä. Sulkeuma-analyysien data voi jäädä hyödyntämättä, jos luokitteluun käytetään yksinkertaisia kriteerejä. Työssä esitetty menetelmä antaa parhaan arvion sulkeumissa olevista faaseista, mikäli sulkeumista ei ole alkuainekarttoja, joiden muodostaminen vie huomattavasti aikaa. Väitöskirjassa esitetään sulkeumien tunnistus- ja luokittelumenetelmän soveltamiskohteita. Menetelmän avulla tutkitaan sulkeumien muutosta ja jakaantumista sulan teräksen näytteenotossa ja sulkeumakuvan muutosta jatkuvavalun aikana. Uutta tietoa esitetään oksidi-sulfidiketjujen muodostumisesta kuumavalssauksen aikana. Tutkituilla teräksillä rikkipitoisuuden noustessa yli 10 ppm:n sulat kalsiumaluminaatit takaisinmuokkautuvat kiinteiksi alumiinioksideiksi tai spinelleiksi jatkuvavalun aikana. Riittävän matalalla rikkipitoisuudella ja kohtuullisella kalsiumkäsittelyllä alumiinioksidien ja spinellien muodostumista voidaan hillitä tai jopa estää se. Tutkimuksessa esitetään, että kuumavalssauksessa venyvimmät sulkeumat muodostavat myös lukuisten sulkeumien oksidi-sulfidiketjuja, jotka ovat tuotteen ominaisuuksien kannalta haitallisia. Tulosten mukaan kalsiumaluminaatit, jotka sulavat matalimmissa lämpötiloissa, eivät kuitenkaan ole taipuvaisimpia venymään valssauksessa. Maltillisella kalsiumkäsittelyllä saavutetaan optimaalinen oksidikoostumus C12A7–CA–MgO-faasiseurueesta. Nämä sulkeumat ovat sulia jatkuvavalussa varmistaen teräksen valettavuuden. Toisaalta ne eivät helposti veny tai rikkoonnu ketjuiksi valssauksessa jatkuvavalun jälkeen.

Há uma demanda por competitividade entre as indústrias de aços, a fim de alcançar a excelência definida pelo termo clean steel. O processo de desgaseificação a vácuo (VD) ocorre durante o Refino Secundário de aços especiais. Sua principal função é remover gases indesejáveis, especialmente o hidrogênio. Entretanto, durante este processo, o fenômeno de flotação e a absorção de inclusões são reportados. O objetivo do presente trabalho foi estudar a viscosidade de escórias e a capacidade da estação de desgaseificação a vácuo do tipo tanque na limpeza de aços sob uma perspectiva industrial. Para realizar este objetivo, foram coletadas amostras de escória e aço antes e após a etapa de vácuo. Os resultados em limpeza de aço foram relacionados à energia de agitação durante o tratamento a vácuo (associada a um parâmetro cinético - βs) e ao efeito da viscosidade de escórias. É possível observar um decréscimo expressivo na população de inclusões entre as condições antes e após tratamento de desgaseificação a vácuo. A remoção de inclusões durante o vácuo atinge 64, 75 e 78% para as faixas de diâmetro de 2,5-5, 5-15 e ≥ 15 μm, respectivamente. Após o processo de desgaseificação, a composição das inclusões não-metálicas aproxima-se da composição química da escória. O processo de agitação na estação de desgaseificação a vácuo promove uma diminuição significativa na densidade de inclusões na faixa de diâmetro de 2,5-15 μm. Além disso, ao aumentar a intensidade do parâmetro cinético, a composição química de inclusões não-metálicas foi afetada e o teor de enxofre presente no aço líquido foi reduzido. Quanto às viscosidades efetiva das escórias, conclui-se que, para valores mais baixos (0,20 Pa.s) aumenta-se a capacidade da escória na remoção de inclusões, enquanto que valores mais altos (> 0,40 Pa.s) aparentaram ser prejudiciais à limpeza do aço. / There is a demand in competitiveness within the steel industry towards achieving excellence defined by clean steel term. The process of vacuum degassing (VD) occurs during the secondary refining of special steels. Its main function is to remove undesirable gases, primarily hydrogen. However, during this process, flotation phenomenon and inclusions absorption are reported. The aim of the present work was to study the slag viscosity and vacuum degassing (tank type) capacity in steel cleanliness from an industry perspective. To achieve this objective, slag and steel samples were taken before and after vacuum stage. The results in steel cleanliness were related to the stirring energy of the vacuum station (associated to a kinetic parameter – βs) and to the effect of slag viscosity. It is possible to observe an expressive decrease in the population of inclusions between the conditions before and after vacuum degassing treatment. The removal of inclusions during the vacuum stage reaches 64, 75 and 78% in the diameter ranges of 2,5-5, 5-15 and ≥ 15 μm, respectively. After the degassing process, the composition of non-metallic inclusions seemed to approach the slags’ chemical compositions. The stirring process in the vacuum degassing station promotes a significant decrease in the inclusion density with 2,5-15 μm diameter range. Also, by increasing the kinetic parameter intensity, the composition of non-metallic inclusions was affected. The sulfur content present in liquid steel was reduced. Regarding the effective viscosities of slags, it was concluded that lower values (0,20 Pa.s) increased slag capacity in inclusion removal, whereas higher values (> 0,40 Pa.s) was detrimental to steel cleanliness.