| 1. |
- Alevanau, Aliaksandr, 1965-
(författare)
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Study of pyrolysis and gasification of biomass from the self-organization perspective
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis focuses on the analysis of kinetics of i) low-temperature pyrolysis of gaseous hydrocarbons, ii) high-temperature steam gasification of char of wood pellets (>700oC), iii) high temperature pyrolysis of straw pellets in an atmosphere of argon and steam, and iv) high temperature pyrolysis of slices of transversally cut wooden sticks. The results of the kinetic measurements in the high-temperature cases are approximated using a least-square based optimization software, which was specially developed to analyse kinetics prone for deviation from the Arrhenius law.In the thesis a general analysis of the researched materials and kinetics of their pyrolysis and gasification is presented from the self-organization perspective. The energy transfer phenomena in both the pyrolysis and gasification processes of biomass are discussed with an emphasis on an analysis of basic phenomena involving the self-organized dynamics on fractal structures in the chosen biomass samples.
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| 2. |
- Liu, Hailong
(författare)
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A Study of the Particle Transport Behavior in Enclosed Environments
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The main purpose of the present work is to increase the fundamental understanding of the particle transport behavior in an enclosed environment and to provide knowledge to the estimate and measure the particle emission from pellets during a steel production process.A laboratory study focused on the effect of the high sliding velocity on the particle generation from dry sliding wheel-rail contacts has been conducted. The particle concentration and the size distribution were acquired online by using particle number counters during the tests. After the completion of each test, the characteristics of pin worn surfaces and collected particles were analyzed with the aid of SEM (scanning electron microscopy) combined with EDS (energy disperse X-ray analysis). The results show that the amount of the particle generation increases significantly as the sliding velocity increases from 0.1 to 3.4 m/s. Moreover, the particle size distribution results indicate that the majority of the generated particles are submicron (ultrafine and fine) particles in the case of a high sliding velocity (1.2 and 3.4 m/s). The observations of iron oxide layers within the pin worn surface and the collected iron-oxide containing particles reveal that these substantial small particles can be attributed to an oxidative wear between the dry sliding wheel-rail contacts under high sliding velocities.The effect of the particle transport behavior with respect to submicron particles in the test chamber on the measurements taken at the outlet was studied by a three dimensional mathematical model. With the assistance of CFD (computational fluid dynamics) simulations, the airflow pattern was found to have a major effect on the particle transport during the tests. By estimating the particle loss rate, 30% of generated particles failed to be captured at the outlet. The reason for that could be a temporary suspension and a deposition onto the surfaces. It should be noted that the particles were assumed to follow the air stream as a result of the small particle size. In addition, the Lagrangian tracking results reveal that the limiting size for particles to become airborne during tests is around 10 µm. However, the computational cost is found to be significant high when the Lagrangian method is adopted.To consider the measurements of micron particles and to reduce the computational time, a coupled drift flux and Eulerian deposition model was developed. In this model, the effects of the gravitational sedimentation and deposition on the particle dispersion were included. The simulation results are in a good agreement with the available experimental data. The value of APD (average percentage deviation) is in the range of 7.7% to 21.2%. Therefore, a set of simulation cases have been carried out to investigate the influential factors (particle size, wall roughness, source location and duration). The results show that the homogeneity of the particle concentration distribution in the model room declines with an increased particle size (0.01 to 10 µm). An almost uniform particle concentration field is formed for submicron particles (0.01 and 0.1 µm) and for fine particles (1 and 2 µm). However, a clear concentration gradient is obtained for coarse particles (4, 6, 8 and 10 µm). This is due to that the gravitational settling dominates the motion of coarse particles. As a result, a large deposited amount and a high deposition fraction was predicted for coarse particles. Moreover, the surface roughness was found to enhance the deposition of submicron particles (0.1 and 0.01 µm) for a given friction velocity. On the contrary, the deposition of micron particles is much less sensitive to the variation of the surface roughness. For a case of an internal source in the room, where a release over a long duration is considered, the particle dispersion strongly depends on the release location. However, this is not the case for a short release time.The dispersions and depositions of micron particles were explored in a laboratory test focused on the particle emission from the wear between the pellets. The simulation results were compared to the measured data with respect to the particle flux at the outlet. A good agreement (4.92% < APD < 12.02%) is obtained. In addition, the influence of the air flow rate at the inlet and the particle size on the sampling results at the outlet was investigated carefully. The results show that a stronger air supply at the inlet can push more particles to the outlet for any given particle sizes. However, the resulted increase of the measurable fraction is more significant for 4, 6, 8 10 µm particles compared to 1, 2 and 20 µm particles. Moreover, it is apparent that 20 µm particles are unable to be measured in such a measurement system.
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| 3. |
- Wang, Jing, 1985-
(författare)
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Development of Graphitic Carbon Nitride based Semiconductor Photocatalysts for Organic Pollutant Degradation
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- As a potential solution to the global energy and environmental pollution, design and synthesis of artificial photocatalysts with high activities have attracted increasing scientific interests worldwide. In recent years, the graphitic carbon nitride (g-C3N4) has shown new possible applications in the photocatalytic field due to its unique properties. However, the photocatalytic efficiency of the pristine g-C3N4 is greatly limited by the high recombination rate of the photo-induced electron-hole pairs. In this thesis, the aim is to design and fabricate efficient g-C3N4 based photocatalysts with enhanced photocatalytic activities under a visible light irradiation.In order to achieve this goal, two strategies have been employed in the present thesis. First, the as-obtained g-C3N4 was used as the host material to construct staggered-aligned composite photocatalysts by selecting semiconductors with suitable band positions. By this method, three kinds of g-C3N4-based composite photocatalysts such as g-C3N4/ZnS nanocage, g-C3N4/m-Ag2Mo2O7 and g-C3N4/MIL-88A were successfully fabricated. Second, the microstructure of the g-C3N4 was modified by the H2O2-treatment at an elevated temperature and ambient pressure.In this study, the g-C3N4 was prepared by a simple pyrolysis of urea. As for all the as-synthesized phtocatalysts, the structures, morphologies and the optical properties were carefully characterized by the following techniques: XRD, SEM, TEM, FT-IR and DRS. Also, the band edge positions of m-Ag2Mo2O7 and MIL-88A were studied by the Mott-Schottky methods. Thereafter, the photocatalytic activities were evaluated by using a solution of rhodamine B (RhB) as a target pollutant for the photodegradation experiments performed under a visible light irradiation. The results showed that all the aforementioned g-C3N4-based photocatalysts exhibited enhanced photocatalytic activities in comparison with the pristine g-C3N4. For the case of the g-C3N4-based composite photocatalysts, the enhancement factor over the pristine g-C3N4 can achieve values ranging from 2.6 to 3.4. As for the H2O2-treated g-C3N4, the degradation rate constant can be 4.6 times higher than that of the pristine g-C3N4.To understand the key factors in new materials design, we also devote a lot of efforts to elucidate the basic mechanisms during the photocatalytic degradation of organic pollutant. Based on the results of the active species trapping (AST) experiments, the main active species in each photocatalytic system were determined. In the g-C3N4/m-Ag2Mo2O7 and the g-C3N4/MIL-88A system, three kinds of active species of ·O2-, h+ and ·OH were found to be involved in the photocatalytic reaction. Among them, the ·O2- and h+ were the main active species. In the g-C3N4/ZnS and H2O2-treated g-C3N4 photocatalytic systems, the main active species was determined as the ·O2-. The reaction pathways of these active species were also demonstrated by comparing the band edge positions with the potentials of the redox couple. In addition, the relationship between the active species and the photocatalytic behaviors of N-de-ethylation and conjugated structure cleavage were studied. Finally, possible mechanisms to explain the enhanced photocatalytic activities were proposed for each photocatalytic system.The results in this thesis clearly confirm that the photocatalytic activity of the g-C3N4 based photocatalyst can efficiently be enhanced by constructions of staggered-aligned composites and by modification of the microstructure of the g-C3N4. The enhanced photocatalytic performance can mainly be ascribed to the efficient separation of the photo-induced electron-hole pairs and the increase of the active sites for the photocatalytic reaction.
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| 4. |
- Ånmark, Niclas, 1987-
(författare)
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Steel characteristics and their link to chip breaking and tool wear in metal cutting
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The vision of this thesis is to study how it is possible to obtain optimised workpieces during metal cutting processes in industry. Specifically, the work is aimed to increase the understanding between the steel characteristics and their link to the chip breaking and tool wear during metal cutting. The emphasis is on the influence of the cleanliness and the characteristics of non-metallic inclusions in the workpiece on the machinability of carburising steel grades. The machinability of a case hardening steel is improved by a M-treatment (additions of Ca). Also, the improved machinability of the M-steels offers an attractive potential to save money which makes it possible to reduce the tooling costs with up to 50%. The improved machinability of Ca-treated steels is correlated to the formation of lubricating slag layers consisting of Ca-enriched sulfide inclusions and oxy-sulfide inclusions, which are formed on the rake face during the machining operation. It is proposed that the formations of slag layers from the workpiece constituents are essential to minimise the chemical degradation of the tool edge due to a contact with the chip. During this process, sulfur minimises the material transfer from the chip flow, whilst Ca-treated impurities have a stabilising effect on the protective deposits made of slag layers.Since there is a remaining industrial need to increase the production rate, whilst maintaining a high quality of the finished parts, the future production will continue to require extreme demands on the quality of workpieces. If the emphasis is focused on the workpiece, it should be possible to obtain a robust manufacturing process. Therefore, the challenge for future steel metallurgists is to develop high performance grades with optimised combined properties.
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| 5. |
- Bai, Haitong, 1986-
(författare)
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A Study of the Swirling Flow Pattern when Using TurboSwirl in the Casting Process
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The use of a swirling flow can provide a more uniform velocity distribution and a calmer filling condition according to previous studies of both ingot and continuous casting processes of steel. However, the existing swirling flow generation methods developed in last decades all have some limitations. Recently, a new swirling flow generator, the TurboSwirl device, was proposed. In this work, the convergent nozzle was studied with different angles. The maximum wall shear stress can be reduced by changing the convergent angle between 40º and 60º to obtain a higher swirl intensity. Also, a lower maximum axial velocity can be obtained with a smaller convergent angle. Furthermore, the maximum axial velocity and wall shear stress can also be affected by moving the location of the vertical runner. A water model experiment was carried out to verify the simulation results of the effect of the convergent angle on the swirling flow pattern. The shape of the air-core vortex in the water model experiment could only be accurately simulated by using the Reynolds Stress Model (RSM). The simulation results were also validated by the measured radial velocity in the vertical runner by the ultrasonic velocity profiler (UVP). The TurboSwirl was reversed and connected to a traditional SEN to generate the swirling flow. The periodic characteristic of the swirling flow and asymmetry flow pattern were observed in both the simulated and measured results. The detached eddy simulation (DES) turbulence model was used to catch the time-dependent flow pattern and the predicted results agree well with measured axial and tangential velocities. This new design of the SEN with the reverse TurboSwirl could provide an almost equivalent strength of the swirling flow generated by an electromagnetic swirling flow generator. It can also reduce the downward axial velocities in the center of the SEN outlet and obtain a calmer meniscus and internal flow in the mold.
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| 6. |
- Bu, Junfu, 1982-
(författare)
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Advanced BaZrO3-BaCeO3 Based Proton Conductors Used for Intermediate Temperature Solid Oxide Fuel Cells (ITSOFCs)
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this thesis, the focus is on studying BaZrO3-BaCeO3 based proton conductors due to that they represent very promising proton conductors to be used for Intermediate Temperature Solid Oxide Fuel Cells (ITSOFCs). Here, dense BaZr0.5Ce0.3Y0.2O3-δ (BZCY532) ceramics were selected as the major studied materials. These ceramics were prepared by different sintering methods and doping strategies. Based on achieved results, the thesis work can simply be divided into the following parts:1) An improved synthesis method, which included a water-based milling procedure followed by a freeze-drying post-processing, was presented. A lowered calcination and sintering temperature for a Hf0.7Y0.3O2-δ (YSH) compound was achieved. The value of the relative density in this work was higher than previously reported data. It is also concluded that this improved method can be used for mass-production of ceramics.2) As the solid-state reactive sintering (SSRS) represent a cost-effective sintering method, the sintering behaviors of proton conductors BaZrxCe0.8-xLn0.2O3-δ (x = 0.8, 0.5, 0.1; Ln = Y, Sm, Gd, Dy) during the SSRS process were investigated. According to the obtained results, it was found that the sintering temperature will decrease, when the Ce content increases from 0 (BZCLn802) to 0.3 (BZCLn532) and 0.7 (BZCLn172). Moreover, the radii of the dopant ions similar to the radii of Zr4+ or Ce4+ ions show a better sinterability. This means that it is possible to obtain dense ceramics at a lower temperature. Moreover, the conductivities of dense BZCLn532 ceramics were determined. The conductivity data indicate that dense BZCY532 ceramics are good candidates as either oxygen ion conductors or proton conductors used for ITSOFCs.3) The effect of NiO on the sintering behaviors, morphologies and conductivities of BZCY532 based electrolytes were systematically investigated. According to the achieved results, it can be concluded that the dense BZCY532B ceramics (NiO was added during ball-milling before a powder mixture calcination) show an enhanced oxygen and proton conductivity. Also, that BZCY532A (NiO was added after a powder mixture calcination) and BZCY532N (No NiO was added in the whole preparation procedures) showed lower values. In addition, dense BZCY532B and BZCY532N ceramics showed only small electronic conductivities, when the testing temperature was lower than 800 ℃. However, the BZCY532A ceramics revealed an obvious electronic conduction, when they were tested in the range of 600 ℃ to 800 ℃. Therefore, it is preferable to add the NiO powder during the BZCY532 powder preparation, which can lower the sintering temperature and also increase the conductivity.4) Dense BZCY532 ceramics were successfully prepared by using the Spark Plasma Sintering (SPS) method at a temperature of 1350 ℃ with a holding time of 5 min. It was found that a lower sintering temperature (< 1400 ℃) and a very fast cooling rate (> 200 ℃/min) are two key parameters to prepare dense BZCY532 ceramics. These results confirm that the SPS technique represents a feasible and cost-effective sintering method to prepare dense Ce-containing BaZrO3-BaCeO3 based proton conductors.5) Finally, a preliminary study for preparation of Ce0.8Sm0.2O2-δ (SDC) and BZCY532 basedcomposite electrolytes was carried out. The novel SDC-BZCY532 based composite electrolytes were prepared by using the powder mixing and co-sintering method. The sintering behaviors, morphologies and ionic conductivities of the composite electrolytes were investigated. The obtained results show that the composite electrolyte with a composition of 60SDC-40BZCY532 has the highest conductivity. In contrast, the composite electrolyte with a composition of 40SDC-60BZCY532 shows the lowest conductivity.In summary, the results show that BaZrO3-BaCeO3 based proton-conducting ceramic materials represent very promising materials for future ITSOFCs electrolyte applications.
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| 7. |
- Chen, Chao, et al.
(författare)
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A Mathematical Modeling Study of the Influence of Small Amounts of KCl Solution Tracers on Mixing in Water and its Residence Time Distribution in a Continuous Flow Reactor-Metallurgical Tundish
- 2015
-
Ingår i: Chemical Engineering Science. - : Pergamon Press. - 0009-2509 .- 1873-4405. ; 137, s. 914-937
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- In an earlier research (Chen et al., 2015a) a mathematical model was established to simulate tracer mixing (a KCl solution). The predicted Residence Time Distribution (RTD) curves showed good agreements with experimental RID curves for larger amounts of tracer additions. However, for smaller additions (50 mL) of a KCl solution into water, the predicted RID curves tended to deviate from the experimental RTD curves for a tundish (a continuous flow reactor). The current paper focuses on the possibilities that the predictability for smaller additions could be resolved by using a suitable turbulence model. The performance of five different turbulence models representing different modeling techniques and levels of complexity were tested in combination with using a density-coupled mixed composition fluid model to simulate the mixing, i.e. the following models: LVEL, Chen-Kim k-epsilon, MMK k-epsilon, Explicit Algebraic Reynolds Stress Model (EARSM), and Large Eddy Simulation (LES): Wall-Adapting Local Eddy-viscosity (WALE). The results indicate that models that tend to resolve turbulence structures renders better predictions of the mixing process of smaller tracer amounts. In addition, the influence of different tracer amounts on the flow in tundish was assessed. The simulation results for 75 mL, 100 mL, 150 mL, and 250 mL KCl tracer additions were compared. The results showed that in an upward flow the tracer will, sooner or later (dependent on the tracer amount), sink to the bottom. This is due to the higher density of the tracer compared to the density of water. From a physical modeling perspective, this issue is like the "butterfly effect". It is showed that for a slight increase of the amount of tracer, the flow field might be disturbed. This, in turn, will result in a shifted RTD curve.
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| 8. |
- Chen, Chao, 1989-
(författare)
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Some Aspects on Macroscopic Mixing in a Tundish
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Two aspects on macroscopic mixing in a continuous flow system – metallurgical tundish were studied. Specifically, 1) the first focus was on salt solution tracer mixing, which is important for tundish design from perspectives of tracer technology and Residence Time Distributions (RTD) as well as for the understanding of the macroscopic mixing in tundishes. The different amounts of salt solution tracer mixing in a tundish were studied by using both physical models and mathematical models. The disturbance of KCl salt tracer on the flow in the tundish with respect to different amounts is like the “butterfly effect”, i.e. only a slight increase of the amount of tracer, the flow field might be disturbed. This, in turn, will result in a shifted RTD curve. 2) The second focus was on Eulerian modeling of inclusions macroscopic transport and removal, which is important for tundish design from perspectives of inclusions removal and to provide information of macroscopic removal of inclusions. In the study, an approach that combined the meso-scale inclusions deposition at turbulent boundary layers of steel-slag interface and the macroscopic transport of inclusions in the tundish was used. The theoretical calculation results showed that the effect of the roughness on the deposition velocity of small inclusions (radius of 1 μm) were more pronounced than that for the big inclusions (up to the radius of 9 μm). The dynamic inclusions removal studies showed that the tundish with a weir and a dam exhibited a better performance with respect to the removal of bigger inclusions (radii of 5 μm, 7 μm and 9 μm) than that of the case without weirs and dams. However, the tundish without weirs and dams showed a higher removal ratio of smaller inclusions (radius of 1 μm).
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| 9. |
- Ekengård, Johan, 1976-
(författare)
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Slag/Metal Metallurgy in Iron and Steel Melts
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this work, the metal and slag phase mixing in three steps of a ladle refining operation of steel melts and for an oxygen balance during cooling of cast iron melts have been studied at two Swedish steel plants and at two Swedish cast iron foundries, respectively. In order to predict the oxygen activity in the steel bulk in equilibrium with the top slag as well as in metal droplets in the top slag in equilibrium with the top slag, three slag models were used. In addition, the assumptions of a sulphur-oxygen equilibrium between steel and slag and the dilute solution model for the liquid steel phase were utilized in the calculations. Measured oxygen activities in steel bulk, which varied between 3.5-6 ppm, were compared to predicted oxygen activities. The differences between the predicted and measured oxygen activities were found to be significant (0-500%) and the reasons for the differences are discussed in the thesis. Slag samples have been evaluated to determine the distribution of the metal droplets. The results show that the relatively largest numbers of metal droplets are present in the slag samples taken before vacuum degassing. Also, the projected interfacial area between steel bulk and top slag has been compared to the interfacial area between the metal droplets and slag.The results show that the droplet-slag interfacial area is 3 to 14 times larger than the flat projected interfacial area between the steel and top slag. Furthermore, the effect of the reactions between top slag and steel and the slag viscosity on the metal droplet formation is discussed. The results show significant differences between the steel bulk and steel droplet compositions and the reasons for the differences are discussed in the thesis. The oxygen activity in different cast irons was studied. Plant trials were performed at three occasions for lamellar, compacted and nodular iron melts. The results show that at temperatures close to the liquidus temperature the oxygen activities were 0.03-0.1 ppm for LGI, around 0.02 ppm for CGI, and 0.001ppm for SGI. In addition, it was found that as the oxygen activities increased with time after an Mg treatment, the ability to form a compact graphite or a nodular graphite in Mg-treated iron melts was decreased. Also, extrapolated oxygen activity differences up to 0.07 ppm were found for different hypoeutectic iron compositions for lamellar graphite iron at the liquidus temperature. Overall, the observed differences in the dissolved oxygen levels were believed to influence how graphite particles are incorporated into the austenite matrix and how the graphite morphology will be in the cast product.
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| 10. |
- Janis, Diana, 1984-
(författare)
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A Study of Different Methods for Inclusion Characterization towards On-line use during Steelmaking
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The interest of gaining on-line information related to non-metallic inclusions during the steelmaking process has recently increased due to the development as well as the promising results of the Pulse Distribution Analysis with Optical Emission Spectroscopy method (PDA/OES). Even though, the time from sampling to presented results on inclusions is only about 5-10 minutes, the method has also shown limitations with respect to the determination of some inclusion characteristics.Therefore, a first step was to perform a study on other methods such as the cross-section method (CS) on a polished sample surface, the cross-section after etching method (CSE), the bromine-methanol extraction method (BME), and the electrolytic extraction method (EE). This study focused on the evaluation of these methods with respect to the time consumption for preparation and analysis of a sample, the analyzed volume and the determination of inclusion and cluster characteristics such as size, number, particle size distribution (PSD) and composition. The CS and CSE methods were found to be suitable in the determination of the largest cluster in a sample which can be recommended in order to select proper extraction parameters for further studies. The BME method was considered to be fast with the possibility of analyzing a large volume. However, the used solution is chemically stronger compared to electrolytic extraction solutions, which can affect the results. In most aspects, the EE method was found to be the most stable, reliable and accurate method with some limitations regarding the time aspect.Based on this conclusion, the EE method was selected for a comparative study with the PDA/OES method. Reliably detected size ranges by using the PDA/OES method were defined for two low-alloyed steel grades. These are 2.0-5.7 μm and 1.4-5.7 μm for steel samples taken before and after a Ca-addition during the secondary steelmaking, respectively. Moreover, agreements between the EE and PDA/OES methods were observed in the average size and number of detected inclusions when only inclusions with the size > 2 μm were considered. Also, a theoretical minimum size and a maximum number ofinclusions present in the steel sample, which can be detected by using the PDA/OES method, were estimated.The work continued by successfully applying the EE method to study correlations between inclusions observed in the liquid steel samples and in a clogged nozzle (clogging material). It was found that the average sizes of spherical and non-spherical inclusions observed in the steel corresponded well with those observed in the clogging material. However, there were some differences in the frequencies of these inclusions. This was explained by a possible transformation of the present inclusions due to a reoxidation and a reaction with the nozzle refractory of the steel melt. The results of this study may contribute in the selection of proper process parameters or inclusion characteristics for future studies on the improvement and application of on-line methods.Finally, suggestions on how to present and interpret data obtained by the PDA/OES method during production of stainless steels were given in the present thesis. More specifically, the possibilities of defining operating windows with respect to inclusion composition and the use of a B-factor for Al (the total content of Al in inclusions detected by using the PDA/OES method) during the secondary steelmaking were discussed. In addition, a correlation study between B-factors for Al and numbers of inclusions (dV > 4 μm) obtained by using the PDA/OES method on process samples, and corresponding slivers indices from plate products was performed. The results showed a moderate correlation between these parameters as well as an increase of the slivers index with increased values of the chosen PDA/OES data. This indicates that it could be possible to predict when there is an increased risk of having slivers on the final rolled product at an early stage of the steelmaking process.
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