KATHOLIEKE UNIVERSITEIT LEUVEN FACULTEIT WETENSCHAPPEN DEPARTEMENT GEOGRAFIE-GEOLOGIE

NON-METALLIC INCLUSIONS IN LIQUID STEEL

Promotoren: Prof. dr. J. Elsen Prof. dr. ir. P. Wollants

Proefschrift ingediend tot het behalen van van de graad van Doctor in de Wetenschappen door Rob DEKKERS

Juni 2002

KATHOLIEKE UNIVERSITEIT LEUVEN FACULTEIT WETENSCHAPPEN DEPARTEMENT GEOGRAFIE-GEOLOGIE

NON-METALLIC INCLUSIONS IN LIQUID STEEL

Examencommissie: Prof. dr. J. Elsen (promotor) Prof. dr. ir. P. Wollants (promotor) Prof. dr. ir. B. Blanpain Prof. dr. P. Muchez (voorzitter) Prof. dr. R. Ottenburgs Dr. C.F. Woensdregt (Universiteit Utrecht)

Proefschrift ingediend tot het behalen van van de graad van Doctor in de Wetenschappen door Rob DEKKERS

Juni 2002

PREFACE
Customers now demand high quality steel, which requires close-tolerance of both steel composition as well as steel cleanliness. Therefore steelmaking processes have to be kept under tight control. Despite of the detrimental effect of inclusions on the steel quality and steel productivity, for an outsider it sounds strange that inclusions are formed on purpose, i.e. during the deoxidation practice. Though most of the oxide particles are removed easily, a relative small amount of them stays in the liquid steel and gives rise to nozzle clogging and loss of product quality. The present research describes non-metallic inclusions in aluminium killed steels produced at the steel plant of Sidmar. Being a geologist my attention is in particular drawn on the morphology of the inclusions. Their morphology depends on the conditions during their formation and growth. Furthermore, impurities, sintering and phase transformations may affect their morphology. During the past years, I have made lots of high resolution scanning electron microscopy micrographs. A number of them have been selected for this booklet in order to introduce you in the magnificent world of micro-crystals. A world full of remarkable shapes, basically aluminium oxide particles grown in a technically pure iron melt. The morphology of inclusions is the red line throughout the book and all aspects concerning the shape of inclusions are considered. The goals of the research were to increase the knowledge on the formation, growth and evolution of non-metallic inclusions in steel and to determine what parameters affect the steel cleanliness. Apart from answering these questions, I hope it will also contribute to mutual respect and exchange of information between scientists and engineers. I am sure that a better understanding may give rise to new ideas. Of course the work would not have been what it is, without the help of colleagues, technicians and friends. I thank the members of the examination committee for their comments, discussions and grammatical corrections. I would like to thank all personnel of Sidmar who have contributed to taking the large amount of steel samples and for their constructive comments and emphasising the topics important for industry. I think most of the technicians at the department have met me, when I came asking for advise or help for specimen preparation, microscope, analysis or other measurements. Finally, I am gratified to all who helped to make this period in and outside the university a nice time. In particular, I thank my roommates, who I bothered with small questions and small calculations. The Flemish Institute for the Promotion of the Scientific Technological Research in Industry (IWT) and Sidmar are gratefully acknowledged for their financial support. And last but not least, I thank my lovely wife Gossina for her patience with me and for her support to keep things organised. Rob Dekkers Leuven, June 2002.

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ABSTRACT
With increasing demands on steel cleanliness, control of non-metallic inclusions becomes more and more important. Non-metallic inclusions mainly result from deoxidation (killing) of the steel with aluminium, which is necessary to prevent formation of CO bubbles during continuous casting. As far as the particles are not captured by the slag, they may appear in the cast steel, where they can cause surface defects or deteriorate the mechanical properties of the steel. In almost all cases inclusions also disturb the continuous casting process. The objectives of the present research are to understand the formation, growth and evolution of non-metallic inclusions during ladle metallurgy and to explain the inclusion morphologies observed in the liquid steel. Moreover, total oxygen measurements of small steel pins, sampled from the liquid steel, were used to evaluate the industrial process parameters that may influence the steel cleanliness. Heats of medium carbon aluminium killed, low carbon silicon-aluminium killed and low carbon aluminium killed steels were sampled with short time intervals during ladle metallurgy. The steel samples were supplied by the steel plant of Sidmar (Gent, Belgium). Furthermore, experiments for different levels of deoxidation were carried out to investigate inclusion formation. Reheating experiments in a hybrid-microwave furnace demonstrated that one type of inclusion is formed due to fast cooling rates. Based on the results of this morphological study of inclusions, it was also shown that the aluminium oxide deposit that causes clogging in submerged entry nozzles is definitely related to the reoxidation of the steel Electrostatic point charge computations, including the short-range interactions, have been carried out to derive the theoretical growth and equilibrium form of spinel and corundum. Also their surface energies have been computed. Non-structural defined shapes have been explained by considering crystal growth mechanisms and parameters that influence growth.

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BEKNOPTE SAMENVATTING
Met de toenemende eisen op het gebied van staalzuiverheid, wordt de controle van nietmetallische insluitsels belangrijker. Deze deeltjes ontstaan tijdens de desoxidatie (rustig maken, kalmeren) van staal met aluminium. Desoxidatie is noodzakelijk om de vorming van CO-bellen te voorkomen tijdens het continu gieten. Voor zover deze insluitsels niet opgenomen worden in de slak, kunnen zij in het staalproduct leiden tot oppervlaktefouten of slechte mechanische eigenschappen. Bijna altijd verstoren insluitsels ook het continu gietproces. Dit onderzoek had tot doel een beter inzicht te verwerven in de vorming, groei en verandering van niet-metallische insluitsels tijdens de panbehandeling, om de insluitselvormen, die aanwezig zijn in het vloeibaar staal, te verklaren. Bovendien werd het totale zuurstofgehalte in het vloeibaar staal gemeten om te onderzoeken welke industrile procesparameters de staalzuiverheid benvloeden. Ladingen van aluminium gekalmeerd staal met gemiddeld koolstofgehalte, aluminium-silicium gekalmeerd laag koolstof staal en aluminium gekalmeerd laag koolstof staal werden met korte tijdsintervallen bemonsterd tijdens de panbehandeling in de staalfabriek van Sidmar (Gent, Belgi). Bovendien werden experimenten voor verschillende mate van desoxidatie uitgevoerd om de insluitselvorming te onderzoeken. Met behulp van het hersmelten van staal in een hybride-microgolfoven werd bewezen dat n type insluitsel gevormd wordt als gevolg van een snelle afkoeling van het staal. Als nevenresultaat van dit onderzoek naar de morfologie van insluitsels kon aangetoond worden, dat de aluminiumoxide afzetting, die aanbering veroorzaakt in de dompelpijp, zonder twijfel gerelateerd is aan de heroxidatie van het staal. Berekeningen met behulp van een elektrostatisch puntladingenmodel, dat ook de korteafstandswisselwerkingen tussen atomen beschouwt, werden uitgevoerd om de theoretische groeivorm en de evenwichtsvorm van spinel en korund af te leiden. Ook hun oppervlakteenergien werden berekend. Insluitselvormen die afwijken van de structuur-bepaalde vorm, werden verklaard door kristalgroeimechanismen en factoren die de groei benvloeden te beschouwen.

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CONTENTS
Notation and units ix

1. Introduction
1.1. Situation of the subject 1.2. Goals of the research 1.3. Outline of the text References 1 3 4 5

2. Non-metallic inclusions in steel: a literature review

2.1. The early days of aluminium deoxidation 2.2. Development of aluminium deoxidation 2.3. Micro-analysis of non-metallic inclusions 2.4. Continuous casting 2.5. Inclusion control by the addition of rare earth elements and calcium 2.6. Morphology of aluminium oxide inclusions 2.7. Conclusions References 7 8 9 11 11 12 14 15

3. Characterisation of inclusions
3.1. 3.2. 3.3. 3.4. 3.5. 3.6. Introduction Total oxygen content of the steel Characterisation of non-metallic inclusions on steel surfaces Extraction of non-metallic inclusions from the steel matrix Size distribution of non-metallic inclusions Preparation of specimens for this research 3.6.1. Extraction method 3.6.2. SEM specimen preparation 3.6.3. Evaluation of extracted inclusions 3.7. Conclusions References 17 17 18 19 20 20 20 21 21 22 23

4. Non-metallic inclusions during industrial practice

4.1. 4.2. 4.3. 4.4. 4.5. 4.6. 4.7. 4.8. Introduction Industrial process description Steel sampling Specimen preparation and analytical techniques Classification of inclusions Evolution of inclusions Relative presence of inclusion shapes Total oxygen content 25 25 26 27 27 28 32 34

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4.9. Discussion 4.10. Conclusions References

35 40 41

5. Deoxidation in low carbon steel killed with aluminium

5.1. Introduction 5.2. Method 5.2.1. Sampling 5.2.2. Sample preparation 5.2.3. Apparatus 5.3. Results 5.3.1. Weight of dual sample 5.3.2. Composition of non-metallic inclusions 5.3.3. Morphology of non-metallic inclusions 5.3.4. Phase of non-metallic inclusions 5.3.5. Heating of inclusions 5.3.6. Failed sampling 5.4. Discussion 5.4.1. Thermodynamic approach 5.4.2. Crystallography and transformation by ion-exchange 5.4.3. Interfacial energy 5.4.4. Transition to corundum 5.5. Conclusions References 43 45 45 46 46 47 47 48 48 50 51 51 52 52 55 57 62 63 64

6. Hybrid-microwave heating of steel

6.1. Introduction 6.2. Methodology 6.2.1. Experimental set-up 6.2.2. The hybrid-microwave heating set-up 6.3. Results 6.4. Discussion 6.5. Conclusions References 65 66 66 66 67 68 70 70

7. Surface modelling of non-metallic inclusions

7.1. Introduction 7.2. The Hartman-Perdok Theory 7.2.1. Periodic Bond Chains (PBCs) 7.2.2. Crystal faces 7.3. Quantitative approach 7.3.1. Attachment energy 7.3.2. Specific surface energy 73 73 73 74 76 76 76

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Contents

7.3.3. The electrostatic point charge model 7.3.4. Theoretical growth form and equilibrium form 7.4. Application on spinel 7.4.1. Structure of spinel 7.4.2. PBC analysis of the normal spinel structure 7.4.3. Surface configurations 7.4.4. Results 7.4.5. Theoretical growth and equilibrium forms 7.4.6. Discussion 7.4.7. Conclusions on spinel 7.5. Application on corundum 7.5.1. PBC analysis of corundum 7.5.2. Results and discussions 7.5.3. Conclusions on corundum 7.6. The interface between inclusion and steel 7.7. Conclusions on the surface modelling of non-metallic inclusions in steel References

77 80 80 80 81 86 90 93 93 96 97 97 97 99 99 104 105

8. Morphology of non-metallic inclusions

8.1. Introduction 8.2. Crystal growth 8.3. Spherical inclusions 8.4. Clusters and dendrites 8.5. Plate-like inclusions 8.6. Polyhedral inclusions 8.7. Accretional growth 8.8. Additional remarks 8.9. Conclusions References 107 108 110 112 114 118 120 121 122 123

9. Submerged entry nozzle clogging

9.1. 9.2. 9.3. 9.4. Introduction Method Results Discussion 9.4.1. Nozzle clogging 9.4.2. Nozzle wear 9.5. Conclusions References 125 126 127 128 128 130 131 131

10. Improvement of steel cleanliness

10.1. Introduction 10.2. Flotation of inclusions 133 133

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10.3. Calcium addition 10.4. Method of aluminium addition 10.5. Filtration 10.6. Slag control 10.7. Role of refractory 10.8. Steel flow control 10.9. Conclusions References

138 139 140 141 145 148 149 150

11. Concluding remarks

11.1. Scientific results 11.2. Industrial application 11.3. Proposal for future work 155 157 158

NOTATION AND UNITS

SYMBOLS
a Al aO
at% Ai Bi c Al cn cO Ci d e D Do
EA EB

activity of aluminium in the steel activity of oxygen in the steel atomic percentage repulsive radii of ion i () softness parameter of ion i () concentration of aluminium particles (numberm-3) concentration of nuclei (numberm-3) concentration of oxygen particles (numberm-3) van der Waals coefficient of ion i (3[kJmole-1]1/2) diameter of inclusion (m) electronvolt (1.60219210-19 J) diffusion coefficient (m2s-1) frequency factor (m2s-1) activation energy for diffusion (Jmole-1) contribution of the Born repulsion to E at (kJmole-1) contribution of the Coulomb interaction to E at (kJmole-1) attachment energy (Jmole-1) crystallisation energy (Jmole-1) partial attachment energy (Jmole-1) slice energy (Jmole-1) total E at (kJmole-1) contribution of the van der Waals interaction to E at (kJmole-1) conversion factor (166.036) standard force (4.184 kJ-1mole-1 ) acceleration of gravity (ms-2) change of Gibbs energy for the formation of a critical nucleus (Jmole-1) change of Gibbs energy for the formation of aluminium oxide (Jmole-1) change of Gibbs energy of reaction (Jmole-1) change of Gibbs energy of the system (J) Boltzmanns constant (1.3810-23 JK-1) constant distance between inclusions (m) melting enthalpy (Jmole-1)

EC E at Ecr Em E sl Etot EvdW f

g * Gn
o G Al 2O3

Gr Gsystem
k K L

Notation and units

qi r rc rij

net charge of ion i radial distance (m) radial distance of critical nucleus (m) interatomic distance between atoms i and j (m) radius of particle (m) universal gas constant (8.314 Jmole-1K-1) radius of metal ion (m) radius of oxygen ion (m) entropy of nuclei (Jmole-1K-1) time (minutes) reaction time (sec.) temperature (K) melting temperature (K) molar volume of inclusion (m3) molar volume (m3) molar volume of steel (m3) volume of a primitive cell (m3) potential at point P mass percentage radius of neck (m) element dissolved in the steel element in oxide number of molecules per primitive unit cell roughening parameter vacancy volume (m-3) constant related to the degree of interaction surface energy (Jm-2) interfacial energy (Jm-2) of pure iron (Jm-2)

R RMe RO
S n t

T Tm Vinclusion Vm Vsteel Vp
VP wt% X X X ox Zp

Fe Fe Al 2O 3 Fe MgAl 2O 4

between steel and corundum (Jm-2) between steel and spinel (Jm-2)
specific surface energy of face (hkl) (mJm-2) of an inclusion (Jm-2) enthalpy contribution to interaction (Jm-2) entropy contribution to
interaction

hkl inclusion enthalpy int entropy int excess int interaction interface

(Jm-2)

excess contribution to interaction (Jm-2) contribution of interaction between two phases to the (Jm-2) of an interface (Jm-2)

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Notation and units

MgAl 2O 4 steel incl . steel incl .

of spinel (Jm-2) of steel (Jm-2)

density of inclusion (kg m-3) density of steel (kg m-3) contact angle standard deviation supersaturation viscosity (Nsm2) emerging velocity (ms-2) orientational factor

CRYSTALLOGRAPHIC SYMBOLS
d hkl (hkl) {hkl} [hkl] hkl (x,y,z)
spacing between two consecutive planes (slice thickness) crystal face or lattice plane crystal form comprising all faces equivalent by symmetry to (hkl) lattice row or zone axis lattice rows or zone axes equivalent by symmetry to [hkl] fractional coordinates of an atom in an unit cell

ACRONYMS
AFM BCF BFDH BSE BOF ccp CMAS EDS EM EPMA hcp HPT IR LCAK LCSAK MCAK OB OES OM Otot Atomic Force Microscopy Burton-Cabrera-Frank (model) Bravais-Friedel-Donnay-Harker (law) Back-Scattered Electron (image) Basic Oxygen Furnace cubic closed packed CaO-MgO-Al2O3-SiO2 Energy Dispersive Spectrometry Electron Microscopy Electron Probe Micro-Analysis hexagonal closed-packed Hartman-Perdok Theory Infra-Red Low Carbon Aluminium Killed (steel) Low Carbon Silicon Aluminium Killed (steel) Medium Carbon Aluminium Killed (steel) Oxygen Blowing Optical Emission Spectrometry Optical Microscopy total oxygen content

Notation and units

xii

PBC PDA pPBC ppm RH SE SEM SEN SPOS STM TEM TOS ULC VKS VOD XRD XRF

Periodic Bond Chain Pulse Discrimination Analysis proto-PBC parts per million Ruhrstahl-Heraeus Secondary Electron (image) Scanning Electron Microscopy Submerged Entry Nozzle Single Particle Optical Sensing Scanning Tunneling Microscopy Transmission Electron Microscopy Total Oxygen Sampling Ultra Low Carbon (steel) Volmer-Kossel-Stranski (model) Vacuum Oxygen Decarburisation X-Ray Diffraction X-Ray Fluorescence

MINERALOGY
corundum galaxite hercynite spinel spinel-type

-Al2O3 MnAl2O4 FeAl2O4 MgAl2O4 (Mg,Mn,Fe,)Al2O4