Study On slag Characterization of EAF High-Cr stainless Steel Making

By Pranesh Rao K M 12PM07F Under the guidance of Dr Mohammed Rizwanur Rahman

Dept. of MME; NITK Surathkal

Contents
Introduction Importance of Slag characterization Experiment Assumptions Sample collection Bulk chemical composition Petro logical analysis of various phases Computational thermodynamics

Introduction
Slags in EAF are product of reaction between oxides and flux Oxides may be present in charge or formed due to reaction of constituent elements present in melt with oxygen Slags being light float on steel melt Hence avoiding oxide inclusion in steel melt

Introduction
Slag characterization involves following steps: Identify the phases at process temperature calculating the amount of the phases investigating the influence of the process parameters on the amount of the phases

Importance of Slag characterization

A good slag practice is essential for production of a high-quality stainless steel The electrical and material efficiency of the electric arc furnace (EAF) can considerably be improved by a good slag practice The metallurgical properties of the slag are strongly influenced by its high-temperature microstructure Depending on composition, Slag can be used for agricultural purposes ,as an additive to cement and as an additive for road construction Hence characterization of the phases within the EAF slag as well as the determination of the amount of these phases is of high importance

Experiment
In order to study the slag characterization in EAF high-chromium stainless steelmaking, slag samples were collected from 14 heats of AISI 304L steel making (18%Cr 10.5% Ni 2%Mn 1%Si 0.03 %C ) two samples per heat Petrographical and thermodynamic characterization was performed on the EAF austenitic steelmaking slags

Assumptions
The slag system consists Al2O3-CaO-Cr2O3 -FeOMgO-SiO2-TiO2 Slag is homogeneous and the slag phases are in equilibrium with each other. The slag temperature was assumed to be 500C higher than the measured steel temperatures. All solid compounds were in their stoichiometric compositions. Basicity =(%CaO)/(%Sio2)

Collection of sample

Collection of slag sample

Slag samplings in the EAF were performed using a long steel spoon Spoon content was poured quickly on the cold concrete floor, freezing the high-temperature microstructure of the slag samples With each slag sampling, the temperature of the steel was measured using temperature lances These were dipped into the steel melt by an automatic sampling system.

Bulk chemical composition

Fragments of each slag sample were randomly chosen and were crushed to powder and compacted onto borate plates The composition of the samples was determined using the X-ray fluorescence spectroscopy As a results an average value of the chemical composition of the bulk of the EAF slagis determined

The composition of the slag samples and the averaged values (AISI 304L), in wt%

Results from Bulk chemical composition determination

Samples 6A-6B and 11A-11B, have a composition near to the averaged composition, with a basicity around 1.5, Thus represent normal EAF operation Samples 8A-8B contain high amount of Cr2O3 compared to average quantity Samples 10A-10B contained higher amounts of MgO and Al2O3 in comparison to the average value Based on above sample slag temperature, Average temperature of A samples: 16750C Average temperature of B samples: 16860C

Petrographical analysis
Petrography was initially performed for the slag samples using light optical microscopy Thereafter, scanning electron microscopy (SEM) using backscattered electrons was done on the samples SEM instruments were equipped with an energy dispersive X-ray spectroscopy (EDS) analyzer to be able to perform a semi-qualitative composition determination on the phases and particles existing in the specimens. X-ray diffraction (XRD) analyses were performed on fine-powdered samples to confirm the existence of the observed phases

Slag specimen preparation for microscopy

Three slag fragments from different parts of one slag sample were collected and mounted in a conductive epoxy resin. Thereafter, the specimens were ground and polished Finally, the surfaces of the specimens were coated with a conductive layer

slag specimen prepared for microscopy

Optical microscopic observations in the slag samples

Darker Matrix Bright large angular particles(>5 m) Bright small angular particles(<5 m) Bright elongated particles Bright dendritic phase Metallic spherical particles Void

Angular particles
Samples 8A and 8B with a higher chromiumoxide content contain both small and large angular particles. Few bright large angular particles(>5 m) were observed in samples 6A-6B and 11A-11B Where as small angular particles were observed in all samples

Optical microscopic image - Large angular particles.

Bright elongated particles

In 6A, 8A-8B,and 10A samples containing high Cr2O3 some elongated particles are also observed

Composition of Angular particles

The chemical composition of the angular particles were analyzed by EDS The result suggests that these particles are mainly composed of Cr ,Mg ,Al ,O The composition and angular shape of these particles correspond to the spinel phase The General formulation of the spinel is A2+B23+O4, A and B are divalent and trivalent cations, respectively Spinels crystallize in octahedral habits, which is the explanation behind the angularity of the cross section of these particles

Ternary oxide system diagram of splines

It was assumed that the spinels are constituted of Cr2O3, MgO and Al2O3 Bold dots in the diagrams represent the compositions of the angular particles Spinel phase area shaded in gray in the diagram Examination of the ternary diagram reveals that the spinel phase area is a solid solution of MgOCr2O3 and MgOAl2O3

Optical microscopy of Metallic spherical particles

These spherical droplets were most likely splashed from the melt bath into the slag layer during the melting process The droplets were classified into three different groups depending on their sizes: i) smaller than 5m, ii) between 5 and 20m iii) larger than 20m The slag contains a large numbers of small droplets. But number of the medium-size droplets was less than that for large-size droplets

Composition of spherical particles

Chemical composition of the droplets for different size classes was analysed using SEM-EDS technique Ni and Cr Wt% in spherical particles is less than that in liuid steel It can be seen that, on average, large droplets contain more Ni and Cr than smaller droplets. Large droplets with a Ni content up to 46 wt% were observed. Cr and Fe have higher affinity to O compared to Ni due to large surface area available in case of large particles Fe and Cr get Oxidized leaving behind Ni

Optical microscopic image of Typical dendrite pattern.

We can observe a typical dendrite-shaped phase in the slag which is brighter than the matrix It is believed that this kind of microstructure is evolved during the solidification period and that it does not exist at process temperatures

Composition of dendrite
SEM-EDS analyses showed that the composition of this phase is very similar to spinel particles. They are mainly composed of Cr, Mg, Al, O. This similarity implies that these dendrites are secondary spinels which have formed during cooling. Size and the shape of the dendrites have been found to be dependent on the cooling rate of samples

COMPUTATIONAL THERMODYNAMICS
The calculations were carried out using ThermoCalc software package. The software was used to predict the equilibrium phases within the slag at the process temperatures using the global slag composition Influence of the parameters such as the slags composition, temperature and basicity on the equilibrium phase assemblage within the slag were studied

Thermodynamic calculations results - Phases theoretically predicted in the slag samples.

MgCr2O4 spinel is assumed to be a stoichiometric compound though it is a solid solution These results are in good agreement with microscopic analyses such as large amount of spinels in 8A-8B samples, absence of spiels in 10B sample

Thermodynamic Calculations Sample 6A

Thermodynamic Calculations Sample 8A

Thermodynamic Calculations Sample 10B

Effect of the process parameters on the amount of spinel particles in the slag

Effect of the process parameters on the amount of spinel particles in the slag

Conclusion
Qualitative and quantitative study of Study On slag Characterization of EAF High-Cr stainless Steel Making is conducted Thermodynamically predicted phases were verified The non convergence of result observed is due to the assumptions made Amount of solid particles (spinels) in slag which determine physical properties of slag is directly related to amount of Cr2O3 in slag

Reference

A Study of EAF High-Chromium Stainless Steelmaking Slags Characteristics and Foamability by Saman Mostafaee Department of Materials Science and Engineering -Royal Institute of Technology Fundementals of steelmaking by E T turkdogan