| 1. |
- Kero Andertun, Jakob
(författare)
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Leaching of water-granulated iron silicate slags and their compounds : A study of synthetic and industrial slag systems
- 2022
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Copper smelter slag is a residue product of the pyrometallurgical extraction of copper. Due to its physical properties, the iron silicate type of copper smelter slag has many possible application areas, e.g., different aggregates and abrasives. During the copper-making process, some copper becomes distributed in the slag; therefore, copper recovery from the slag is commonly done through slag treatment processes. Despite treatment, copper-containing inclusions can remain in the final slag. In order to secure the environmental properties of slags containing inclusions, the leaching mechanisms needs to be understood, which is the focus of the thesis presented.Synthetic and industrial iron silicate slags have been studied with respect to the impact of the slag constituent’s oxide (glass), sulfide (matte) and metalloids (speiss) on leaching as well as the impact of chemical composition (ZnO and CaO content). The synthetic slags are melted in laboratory furnaces. The industrial slags have undergone a Zn-fuming and settling process (including CaO additions for some slags) to recycle and reduce the zinc content and further separate copper-containing inclusions such as sulfide (matte) and metalloid (speiss) species. The materials investigated in the thesis are solidified using water granulation.All materials are characterized by their chemical compositions and mineralogy. Further, industrial slag constituents are investigated regarding their leaching contribution. Syntheticiron silicate (oxide) is investigated regarding the influence of ZnO content and granulation temperature on Zn leaching. CaO-modified industrial iron silicate slags are investigated regarding the leaching of specific elements (e.g., Cu, Zn, Ni, As, Sb). The leaching tests examine the effect of pH, oxidation and time using water leaching, acid and oxidating leaching and dynamic leaching methods.Characterizing the slag constituents shows that the glass mainly contains amorphous iron silicate. The matte contains mainly copper sulfides, and speiss contains copper metalloids. The leaching results show that the glass contributes to Cu and Zn leaching at pH 8.4, and the speiss contributes to Ni and Sb leaching at pH 7.8. Further, the leaching contribution of matte and speiss increased with decreasing pH. The main leaching elements from the matte and speiss include Cu, Ni, As and Sb.Characterization of the ZnO-modified iron silicate shows that Zn is mainly distributed in glass and partly in fayalite. Further, the Zn leaching increases with granulation temperature, ZnO content in the glass and decreasing pH.Characterization of CaO-modified slags shows that up to 20 wt.% CaO dissolves into the glass phase. An increased CaO content resulted in increased Ca leaching, yielding higher pH. Leaching of Zn, Cu, Ni and Sb was on the other hand shown to decrease. Further, long-term leaching studies confirm increasing pH and Ca leaching. In contrast, the leaching of Cu, Zn and Ni showed a peak after a certain time, which was lowered with increasing CaO content in the slags. The leaching of As and Sb increased with increasing leaching time, but the increase diminished with increasing CaO content in the slags. A lower pH and an oxidating environment increased the leaching of Zn, Cu and Ni.The summarized results from this thesis indicate that the glass contributes to Zn leaching while copper-containing inclusions matte and speiss contribute to the leaching of Cu, Ni, As and Sb. The leaching of elements from the copper-containing inclusions matte and speiss can be limited by ensuring a pH buffer preventing acidification, for example, by CaO modification. CaO modifications decrease the slag leaching resistance, which contributes to increasing pH in the leachate by Ca-dissolution and hence decreased leaching of copper-containing inclusions in the slag. Also, the Zn leaching from the slag decreased with increasing pH in the leachate.
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| 2. |
- Deng, Zhiyin
(författare)
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Study on the Interaction between Refractory and Liquid Steel Regarding Steel Cleanliness
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The present thesis focuses on the interaction between refractory and liquid steel. The aim of this work is to understand the interaction behavior between refractory and liquid steel regarding steel cleanliness. The effect of different refractories on different inclusions in Al-killed steel was studied in a furnace. The sintering mechanism of filler sand were also investigated in laboratory. In the industrial trials, the attachments of different oxides on the walls of submerged entry nozzle (SEN) were discussed in the cases of high strength low alloy steel (HSLA) and ultra-low carbon steel (ULC).It is found that the effect of alumina and spinel refractory on all the three types of inclusions is very little, while MgO refractory influences the inclusions depending on the activity of dissolved oxygen in liquid steel. At low oxygen level, alumina inclusions could transform into spinel inclusions with the help of MgO refractory, while the effect on spinel and calcium aluminate inclusions is not evident. On the other hand, when the activity of dissolved oxygen is high enough, the evolution of spinel inclusions from alumina inclusions could not be seen.The reaction between chromite and silica grains leading to liquid formation is the main mechanism for the sintering of filler sand. The factors viz. steel composition, silica size and content, operation temperature and process holding time have a strong influence on the sintering of the filler sand. Smaller size and higher content of silica in sand, steel grades containing higher Mn and Al contents, higher temperature and longer holding time would result in serious sintering. The choice of the sand needs to take those factors into account.The results show that solid alumina particles are always agglomerated on the inner wall of SEN in the case of ULC steel. The top slag with high FeO and MnO contents is considered as the main reason of this kind of attachments. The removal of slag might be a good method to avoid the attachments. In the case of HSLA steel, liquid calcium aluminate inclusions could attach on the inner wall of SEN as well. The smoothness of the inner wall of the SEN holds the key of liquid attachments. In addition, the attachment situation on the outer wall of SEN depends on the operations. The oxygen entrainment through the mold powder would result in the formation of plate-like alumina attachments. The control of reoxidation due to oxygen entrainment would help to avoid this situation.
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| 3. |
- Wang, Yong, 1990-
(författare)
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Characterization of Impurities in Different Ferroalloys and Their Effects on the Inclusion Characteristics of Steels
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Ferroalloys have become increasingly important due to their indispensable role in steelmaking. As the performance requirements of steel materials increase, it is necessary to have a better understanding of the impact of impurities in ferroalloys on the steel cleanliness. The quality of the ferroalloy will directly affect the quality of the steel. This is especially important when ferroalloys are added during the late stage of the ladle metallurgy process. The goal of the present work is to gain knowledge about various ferroalloy impurities added in the steel production process and to study the influence of ferroalloy impurities on inclusions in the steel. The research work is divided into four main parts.In the first part, previous works on impurities present in different ferroalloys as well as how these impurities can influence the steel cleanliness have been reviewed. The applications of different ferroalloys and their production trends were discussed. The possible harmful inclusions in different ferroalloys were identified. The results showed that: 1) MnO, MnSand MnO-SiO2-MnS inclusions from FeMn and SiMn alloys have a temporary influence on the steel quality; 2) The effect of trace elements, such as Al, Ca contents, should be considered before the addition of FeSi alloys to steel. Also, Al2O3 inclusions and relatively high Al contents are commonly found in FeTi, FeNb and FeV alloys due to their production process. This information should be paid more attention to when these ferroalloys are added to steel; and 3) specific alloys containing REM oxides, Cr(C,N), Cr-Mn-O, Al2O3, Al-Ti-O, and Ti(C,N) have not been studied enough to enable a judgement on their influence on the steel cleanliness. Moreover, the effect of large size SiO2 inclusions in FeSi and FeMoalloys on the steel cleanliness is not fully understood.In the second part, the impurity assessment of 10 different ferroalloys (FeSi, FeCr, FeMo,FeV, FeTi, FeNb, FeW, FeB, MnN, FeCrN) was carried out by using various characterization techniques. The inclusions obtained in these ferroalloys were mostly silica or alumina, or the oxides of the base elements. Also, the main elemental impurities and inclusions were closely related to their manufacturing route. The advantages and disadvantages of different methods were compared, and the detection technology of ferroalloy inclusions was optimized. The results showed that the traditional two-dimensional method on a polished surface cannot always be applied for the investigation of inclusions in some specific ferroalloys. Moreover, the investigations of inclusions on metal surface after electrolytic extraction showed a big potential to use to detect larger sized inclusions. The results on both the film filter and metal surface should be grouped together to obtain more comprehensive information on the inclusion characteristics. Among these ferroalloys, FeCr and FeNb were found to be relatively less studied ferroalloys. Thus, they were selected for further studies.In the third part, the early melting behaviours of FeNb, HCFeCr and LCFeCr alloys during additions in liquid iron was studied. The experiments were carried out by using the"liquid metal suction" technique. Here, the ferroalloy was contacted with liquid iron for a predetermined time and then quenched. The obtained samples were further studied to determine the microstructure and the formation of inclusions. It was found that the mutual diffusion between solid ferroalloy and liquid iron formed a reaction zone. Also, the initial dissolution mechanism of FeNbs alloy in liquid iron was proposed, and the mechanism was controlled by diffusion. The TiOx inclusions in FeNb alloy will partially or completely be reduced due to a reaction with Nb in the reaction zone. The original stable inclusions, such as Al2O3 in FeNb alloys and MnCr2O4 inclusions in LCFeCr alloys can move in this zone and keep their original forms without experiencing any changes. Under the same conditions, the melting speed of LCFeCr alloy is faster than that of HCFeCr alloy. The addition of FeNband FeCr alloys in steel certainly introduces inclusions to steel.In the fourth part, the influence of the addition of LCFeCr alloys on the inclusions in Ti containing ferritic stainless steel was studied on a laboratory scale. It was found that the theMnCr2O4 inclusions in the LCFeCr alloy would react with TiN and dissolved Ti in the Ti containing steel to form TiOx-Cr2O3 system inclusions. In addition, the removal effect of slag on such inclusions was also studied. The results found that the slag addition can modify their-rich inclusions, but that the Ti content in the steel was significantly reduced. Therefore, a proper amount of TiO2 content should be added into the slag to get a low Ti loss in the steel melt, which should be studied further. Therefore, the composition of the steel directly affects the behaviour of the inclusions from ferroalloys in steel.
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| 4. |
- Adolfsson, Daniel
(författare)
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Cementitious properties of steelmaking slags
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The present study is directed towards the use of steelmaking slags as raw material for sulphoaluminate belite cement (SAB). Another important objective was to characterise the cementitious properties of phases in ladle furnace slag (LFS) specifically the calcium aluminates. Mayenite (C12A7) is considered one of the most important calcium aluminate in LFS, and since comparatively limited data on the kinetic properties of this phase are available, it was decided to study C12A7 more closely with regard to both particle size and temperature sensitivity. The behaviour of high-temperature reactions of tested SAB mixtures was investigated using thermogravimetric analysis coupled with a quadrupole mass spectrometer. Mineralogical observations were carried out with x-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The results proved that steelmaking slags have the potential to work as raw material, since sulphoaluminate (C4A3 S ) along with polymorphs of dicalcium silicate (C2S) and ferrite phase (C4AF) were detected after firing at 1200ºC in an air atmosphere. The hydration properties of the specimens were analysed through conduction calorimetry, and compressive strength of specimens hydrated for 2 and 28 days. The compressive strength was in accordance with that suggested in the literature for slow hardening SAB cement. Both mixtures tested behaved the same with regard to heat development as well as the amount of ettringite (AFt) formed during the first 24 hours of the hydration. The formation of AFt was characterised with both differential scanning calorimeter (DSC) and XRD. The crystallographic distribution in LFS samples was quantified using Rietveldanalysis. Calorimetric studies were performed at 20, 25 and 30°C in order to calculate the activation energy of hydration and thereby to suggest a kinetic model for tested compositions within this temperature interval. In addition to heat of hydration, compressive strength tests were completed on mortar prisms of LFS, and LFS in a blend with ground granulated blast furnace slag (GGBFS) which hydrated for 2, 7 and 28 days. Both compositions reached acceptable early strengths, whereas, after 28 days hydration, the blend was superior to neat LFS. Related activation energy was according to the Avrami-Erofeev model determined to 58 kJ/mol for the LFS and 63 kJ/mol for the blend. Corresponding calorimetric studies at the same temperatures were performed on a fine and coarse size fraction (Fraction A and Fraction B) of a synthesised C12A7. The purity was confirmed by XRD, and the hydraulic behaviour was investigated in excess water with respect to the dissolution. The apparent activation energy was calculated to 33 and 79 kJ/mol, respectively, for Fractions A-B using the Avrami-Erofeev model. From the model, it was also concluded that the acceleration period can be ascribed to a phase-boundary controlled mechanism. The principal calcium aluminate hydrates obtained were C2AH8 and C2AH7.5, and it was further observed that C12A7 is accompanied by an anomalous setting behaviour much like monocalcium aluminate (CA), and that the decomposition of C2AH8 to C2AH7.5 develops more slowly with higher surface area, specifically at 20 and 30°C.
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| 5. |
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