Inclusion Characterization in High Strength Low Alloy Steel

by

Chao Peng Paul Wu

A thesis submitted in conformity with the requirements for the degree of Master of Applied Science Graduate Department of Materials Science and Engineering University of Toronto

Copyright by Chao Peng Paul Wu, 2009

Inclusion Characterization in High Strength Low Alloy Steel

by Chao Peng Paul Wu

Master of Applied Science Department of Materials Science and Engineering University of Toronto 2009

ABSTRACT
The cleanliness of high strength low alloy (HSLA) steel was assessed qualitatively and quantitatively. The determination of inclusion type and inclusion morphology were carried out using Selective Potentiostatic Etching by Electrolytic Dissolution (SPEED) method allowing in-situ examination of inclusion morphology by analytical techniques such as SEM/EDS. Inclusion size analysis mainly involved a combination of an analytical technique to provide images of the sample surface and an image analysis system to accurately measure the inclusion size. Four analytical methods were compared in order to evaluate their suitability for subsequent quantitative analysis. It was found that images taken with backscattered electron imaging mode from the scanning electron microscope provides the most accurate representation of inclusion distribution. The various techniques were used to evaluate HSLA steel grades of similar chemistry produced with and without gas shrouding. The results confirmed that with reoxidation minimized by gas shrouding between ladle and tundish, the steel cleanliness was significantly improved. ii

ACKNOWLEDGEMENTS

I owe my deepest gratitude to my supervisor, Professor A. McLean, whose encouragement, guidance, and support have motivated and inspired all his students, myself included. I would like to express my sincere thanks to my mentors, Dr. Y.D. Yang and Dr. H. Soda for their constant assistance and encouragement during the term of this project. This thesis would not have been possible without the helpful discussions. I admire Dr. Yangs passion for research and his meticulous approach to questions, which have taught me much. I am indebted to Dr. Soda, who always manages to make himself available to give counsel on all aspects. I would like to extend my thanks to the research group members for the moral support and friendship. Appreciation is also expressed to the staff of the MSE department for the technical and administrative support during the course of the project. Financial support from Natural Sciences and Engineering Council of Canada and University of Toronto fellowship is greatly appreciated. I would also like to thank Gerdau Ameristeel Inc. for providing me with the steel samples. I am especially grateful to Mr. S. Paul at Gerdau Ameristeel Inc. for his helpful advice and assistance. Finally, I would like to thank my family and friends for their immense support and encouragement throughout my study.

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TABLE OF CONTENTS
ABSTRACT........................................................................................................................ ii ACKNOWLEDGEMENTS ............................................................................................... iii TABLE OF CONTENTS................................................................................................... iv LIST OF FIGURES ........................................................................................................... vi LIST OF TABLES ............................................................................................................. ix NOMENCLATURE ........................................................................................................... x CHAPTER ONE: INTRODUCTION ................................................................................. 1 1.1 Introduction and Background ............................................................................... 1 1.2 References ............................................................................................................. 3 CHAPTER TWO: LITERATURE REVIEW ..................................................................... 4 2.1 Melting and Casting Operations ........................................................................... 4 2.2 Steel Deoxidation .................................................................................................. 6 2.2.1 Thermodynamics of deoxidation ............................................................... 6 2.2.2 Single component deoxidation................................................................... 8 2.2.3 Multi-component deoxidation.................................................................. 12 2.3 Manganese Oxide Silicon Oxide Aluminum Oxide System......................... 17 2.4 Classification of Non-Metallic Inclusions .......................................................... 19 2.4.1 Based on inclusion chemistry and composition ....................................... 19 2.4.2 Based on inclusion formation mechanism ............................................... 22 2.5 References ........................................................................................................... 23 CHAPTER THREE: EXPERIMENTAL ASPECTS........................................................ 24 3.1 Overview ............................................................................................................. 24 3.1.1 Sample preparation .................................................................................. 25 3.2 Qualitative Assessment ....................................................................................... 26 3.2.1 Inclusion morphology examination (SPEED method[1]) ......................... 26 3.2.2 Inclusion species analysis ........................................................................ 28 3.3 Quantitative Assessment ..................................................................................... 29 3.3.1 Image acquisition ..................................................................................... 29 3.3.2 Image analysis.......................................................................................... 31 iv

3.4 References ........................................................................................................... 34 CHAPTER FOUR: RESULTS AND DISCUSSION ....................................................... 35 4.1 Qualitative Assessment ....................................................................................... 35 4.1.1 Al2O3 (Alumina) ...................................................................................... 35 4.1.2 SiO2 (Silica) ............................................................................................. 41 4.1.3 MnO (Manganosite) ................................................................................. 46 4.1.4 MnO-SiO2 (Rhodonite) ............................................................................ 47 4.1.5 MnO-Al2O3 (Galaxite) ............................................................................. 50 4.1.6 CaO-Al2O3 (Calcium aluminate) ............................................................. 52 4.1.7 CaO-SiO2 (Calcium silicate) .................................................................... 59 4.1.8 CaO-Al2O3-SiO2 (Calcium aluminosilicate) ............................................ 61 4.1.9 MnS (Manganese sulphide) ..................................................................... 63 4.1.10 Development of inclusion species during steelmaking.......................... 69 4.2 Quantitative Assessment ..................................................................................... 72 4.2.1 Particle size distribution........................................................................... 73 4.2.2 Maximum particle size............................................................................. 76 4.2.3 Inclusion area fraction.............................................................................. 78 4.2.3 Backscattered electron image analysis (BSE-IA) in steel cleanliness study ......................................................................................................................... 80 4.3 References ........................................................................................................... 81 CHAPTER FIVE: CONCLUSIONS ................................................................................ 82 5.1 Conclusions ......................................................................................................... 82 5.2 Future Work ........................................................................................................ 83 APPENDICES .................................................................................................................. 84 Appendix A: Inclusions Effect on Fatigue Behaviour............................................. 84 Appendix B: Inclusion Particle Size Distribution of 1018S Samples....................... 85 Appendix C: Inclusion Particle Size Distribution of A529 Samples ........................ 88

LIST OF FIGURES
Figure 2-1: Schematic of melting and casting operations in steelmaking[2] ....................... 5 Figure 2-2: Free energy of formation for various oxides. Dash-dot line indicates equal oxygen pressure in unit of atmosphere[4] .................................................................... 7 Figure 2-3: Deoxidizing power of various elements at 1600C[5] ...................................... 7 Figure 2-4: a) As-polished (2-dimensional) steel sample showing Al2O3 dendrite b) Partial slime extracted (3-dimensional) steel sample showing the same Al2O3 dendrite[1] .................................................................................................................. 11 Figure 2-5: Equilibrium relations for manganese-silicon deoxidation of steel at various temperatures[3] ........................................................................................................... 13 Figure 2-6: The effect of manganese content on stability of oxide phases resulting from steel deoxidation at 1550C (m: mullite; l: liquid manganese silicate)[9] ................. 15 Figure 2-7: CaO-Al2O3 equilibrium phase diagram[10] ..................................................... 16 Figure 2-8: Schematic representation of MnO-SiO2-Al2O3 ternary phase diagram[6] ...... 17 Figure 2-9: Free energy of formation for various sulphides. Dash-dot line indicates equal sulphur pressure in unit of atmosphere[4] .................................................................. 21 Figure 3-1: Flow chart of the scheme of experiments ...................................................... 24 Figure 3-2: Sampling locations ......................................................................................... 25 Figure 3-3: Schematic of SPEED apparatus [1] ................................................................ 27 Figure 3-4 Anode polarization curve ................................................................................ 28 Figure 3-5: Images acquired using (a) optical microscopy, (b) laser confocal microscopy, (c) SEM (secondary electron mode) and (d) SEM (backscattered electron mode) .. 32 Figure 3-6: Photograph processed by image analysis showing detected area as inclusions (a) laser confocal microscopy, (b) SEM (backscattered electron mode) .................. 33 Figure 4-1: Oxide inclusions found in 1018S ladle sample: alumina ............................... 36 Figure 4-2: Oxide inclusion found in A529 billet sample: alumina dendrites .................. 36 Figure 4-3: Oxide inclusions found in A529 ladle sample: a) alumina and galaxite (G) . 37 b) alumina cluster.............................................................................................................. 37 Figure 4-4: Glassy Al2O3 (globular) inclusions found in 1018S furnace tap sample ....... 39 Figure 4-5: Glassy Al2O3 (plate) inclusions found in 1018S ladle sample ....................... 39 vi

Figure 4-6: Oxide inclusions in steel: corundum in a) manganese aluminosilicate matrix [1018S ladle tap sample] b) calcium aluminate matrix [A529 tundish sample] ....... 40 Figure 4-7: Oxide inclusion in A529 billet sample: cristobalite (K) in rhodonite (R) ..... 42 Figure 4-8: Oxide inclusion in A529 billet sample: rhodonite (R), low quartz (Q), tridymite (T) and glassy silica (A) ............................................................................ 43 Figure 4-9: Oxide inclusion in A529 tundish sample: cristobalite (K) in rhodonite (R) matrix, and glassy silica (A) ..................................................................................... 44 Figure 4-10: Oxide inclusion in 1018S tundish sample: low quartz (Q) and tridymite (T) ................................................................................................................................... 45 Figure 4-11: Oxide inclusion in 1018S billet sample: low quartz (Q).............................. 45 Figure 4-12: Oxide inclusion in A529 billet sample: manganosite .................................. 46 Figure 4-13: Oxide inclusions found in A529 ladle tap sample: rhodonite ...................... 47 Figure 4-14: Oxide inclusions found in A529 billet sample: rhodonite (R) and cristobalite (K) ............................................................................................................................. 48 Figure 4-15: Oxide inclusions found in A529 billet sample: rhodonite (after rolling)..... 49 Figure 4-16: Oxide inclusions found in 1018S ladle sample: rhodonite .......................... 49 Figure 4-17: Oxide inclusions found in A529 furnace tap sample: galaxite (G) .............. 50 Figure 4-18: Oxide inclusions found in 1018S ladle tap sample: galaxite (G) and chromium galaxite (Cr G) ......................................................................................... 51 Figure 4-19: Oxide inclusions found in 1018S ladle tap sample: calcium aluminate ...... 52 Figure 4-20: Oxide inclusions found in 1018S furnace tap sample: calcium aluminate (CA) and galaxite (G) ............................................................................................... 54 Figure 4-21: Oxide inclusions found in A529 ladle sample: calcium aluminate (CA) .... 55 Figure 4-22: Oxide inclusions found in A529 furnace tap sample: calcium aluminate.... 56 Figure 4-23: Oxide inclusions found in 1018S ladle tap sample: calcium aluminate ...... 56 Figure 4-24: Oxide inclusions found in A529 tundish sample: calcium aluminate .......... 57 Figure 4-25: Oxide inclusions found in 1018S ladle sample: calcium aluminate ............ 57 Figure 4-26: Oxide inclusions found in 1018S ladle sample: calcium aluminate ............ 58 Figure 4-27: Oxide inclusions found in 1018S ladle sample: calcium aluminate with high silica content ............................................................................................................. 58 Figure 4-28: Oxide inclusions found in 1018S billet sample: calcium silicate ................ 59 vii

Figure 4-29: Oxide inclusions found in 1018S furnace tap sample: calcium silicate (CS) and corundum (C) ..................................................................................................... 60 Figure 4-30: Oxide inclusions found in A529 tundish sample: calcium silicate .............. 61 Figure 4-31: Oxide inclusions found in A529 ladle tap sample: calcium aluminosilicate 62 Figure 4-32: Oxide inclusions found in 1018S ladle sample: calcium aluminosilicate.... 63 Figure 4-33: Sulphide inclusions found in 1018S billet sample: manganese sulphide..... 64 Figure 4-34: Sulphide inclusions found in 1018S billet sample: manganese sulphide..... 65 Figure 4-35: Sulphide inclusions found in A529 billet sample: manganese sulphide ...... 66 Figure 4-36: Sulphide inclusions found in A529 billet sample: manganese sulphide ...... 67 Figure 4-37: Sulphide inclusions found in A529 billet sample: manganese sulphide additional morphologies............................................................................................ 67 Figure 4-38: Sulphide inclusions found in 1018S billet sample: manganese sulphide scale (S) around silicate matrix (M)................................................................................... 68 Figure 4-39: Sulphide inclusions found in 1018S billet sample: manganese sulphide scale (S) around silicate matrix (M)................................................................................... 69 Figure 4-40: Inclusion size distribution of 1018S............................................................. 74 Figure 4-41: Inclusion size distribution of A529 .............................................................. 74 Figure 4-42: Comparison of total inclusion count ............................................................ 75 Figure 4-43: Maximum particle size plot of 1018S steel samples .................................... 76 Figure 4-44: Maximum particle size plot of A529 steel samples ..................................... 77 Figure 4-45: Comparison of maximum particle size ........................................................ 77 Figure 4-46: Inclusion area fraction of 1018S steel samples ............................................ 78 Figure 4-47: Inclusion area fraction of A529 steel samples ............................................. 79 Figure 4-48: Comparison of inclusion area fraction ......................................................... 79 Figure 5-1: Proposed levitation apparatus ........................................................................ 83

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LIST OF TABLES
Table 2-1: Cleanliness requirements for steel products[1] ................................................... 4 Table 2-2: Stoichiometric composition of reported inclusion phases in Figure 2-8[6]...... 18 Table 2-3: Inclusion phases found in MnO-SiO2-Al2O3, FeO-SiO2-Al2O3, and MnO-SiO2Cr2O3 systems[6] ........................................................................................................ 19 Table 3-1: Specimen chemical composition ..................................................................... 25 Table 4-1: Summary of inclusion types present in A529 steel ......................................... 70 Table 4-2: Summary of inclusion types present in 1018S steel ........................................ 70 Table A: Coefficient of thermal expansion of various inclusion types[2] ......................... 85

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NOMENCLATURE
Symbols ax d G K T T[O] Activity of x Maximum particle size Free energy of formation Equilibrium constant Temperature Total oxygen Wavelength Coefficient of thermal expansion K ppm m K-1 m kCal Units

Element Abbreviations Al C Ca Cu Cr Fe O P Pt Mg Mn N Ni S Si Aluminum Carbon Calcium Copper Chromium Iron Oxygen Phosphorus Platinum Magnesium Manganese Nitrogen Nickel Sulphur Silicon

Compound Abbreviations Al2O3 CaO CaOAl2O3 CaOAl2O3SiO2 CaO SiO2 CaS FeO FeOAl2O3 FeS MgO MnO MgOAl2O3 MnOAl2O3 MnOSiO2 MnS SiO2 Alumina Calcia Calcium aluminate Calcium aluminosilicate Calcium silicate Calcium sulphide Wstite Hercynite Troilite Periclase Manganosite Spinel Galaxite Rhodonite Manganese sulphide Silica

Abbreviations ASTM BSE DIC EAF EDS HSLA IA LCM LIMCA MIDAS American Society for Testing and Materials Backscattered Electron Differential Interference Contrast Electric Arc Furnace Energy Dispersive Spectrometry High Strength Low Alloy Image Analysis Laser Confocal Microscope Liquid Metal Cleanliness Analyzer Mannesmann Inclusion Detection by Analysis Surfboards xi

OES OM PDA ppm SE SEN SEM SPEED wt%

Optical Emission Spectrometry Light-Optical Microscope Pulse Discrimination Analysis parts per million Secondary Electrons Submerged Entry Nozzle Scanning Electron Microscope Selective Potentiostatic Etching by Electrolytic Dissolution weight percent

xii

CHAPTER ONE: INTRODUCTION

1.1 Introduction and Background The standards governing steel cleanliness vary among different applications of the final product. With decreasing product cross-sectional dimension, such as thin strip steel, the presence of critically sized inclusions has increasing effects on product performance hence the rising cleanliness requirements for steel quality in recent decades. Inclusion particle size distribution is frequently used to provide characteristic description of steel cleanliness. A comprehensive cleanliness evaluation also requires complementary information on non-metallic inclusions found such as quantity, spatial distribution, type, and morphology. With the growing demand for high quality materials, the cleanliness of different steel types has become very important. High strength low alloy (HSLA) steels offer improved weldability, and superior mechanical and corrosion-resistant properties compared to mild or low carbon steel at a minor price premium.[1] Load-bearing HSLA steel found in structural applications is susceptible to fatigue failure initiated by non-metallic inclusions. However, very little is known about the types and amounts of inclusions present in this class of steel. The great challenge faced by steelmakers, at the present, is the lack of reliable cleanliness assessment methods to quickly evaluate the quality of steel products at low cost. The cleanliness assessments performed traditionally using metallurgical microscopy, chart comparison, and visual inspection of semi-finished products no longer give adequate feedback in regard to micro-cleanliness. Image analysis is a powerful tool in assessing steel cleanliness with improved efficiency and accuracy. However, it has been reported[2] that with automated image analysis using optical microscopy there exists a common problem of potential erroneous detection of defects arising from inadequate sample preparation.

In general, inclusion generation can be classified into two sources, indigenous and exogenous. Oxide particles are formed as a result of deoxidizer additions made to the steel ladle as a means to reduce the level of dissolved oxygen in the liquid steel. If these deoxidation products are not removed from the steel prior to casting, they will be present as oxide inclusions in the steel product. The inclusions generated via this process are inherent to the steelmaking process, and therefore are indigenous in nature. Exogenous source of inclusions may arise from uncontrolled oxidation of liquid steel (reoxidation) as well as excessive melt stirring resulting in slag entrainment and refractory erosion. Indigenous inclusions usually have modest influence on material properties due to smaller particle size. They can only be minimized through process control but cannot be eliminated completely. On the other hand, macro-inclusions with exogenous origin are detrimental to various material properties. However, generation of exogenous inclusion is largely practice-dependent and can be avoided by implementing suitable procedures and careful control.[3] There are various sources that can promote the formation of macro-inclusions throughout the different steelmaking operations.[4] Reoxidation is often responsible for the generation of macro-inclusions. Liquid steel is especially vulnerable to reoxidation by the atmosphere during vessel transfer if the stream is allowed to come into contact with air. Therefore, the cleanliness assessment must indicate the processing step that results in the generation of these harmful inclusions in order to prevent their formation and facilitate the removal process. The aim of this investigation is to characterize and quantify the inclusions found in HSLA steel using novel procedures. The specific objectives of this thesis are as follows: To provide a time-efficient and reliable method to assess the cleanliness of steel. To evaluate and compare analytical methods for acquiring images that can accurately represent the distribution of inclusions in a given sample. To establish the origin of various inclusion species. To identify the vulnerable processing stage during secondary steelmaking operations that result in detrimental inclusion generation. 2

To examine the effect of melt protection on the cleanliness of steel products.

1.2 References [1] W.D. Callister, Materials Science and Engineering An Introduction, John Wiley & Sons, Inc., New York, NY, 2003, 6th edition, p.336 [2] S. Johansson, Inclusion assessment in steel using the new Jernkontoret Inclusion Chart II for quantitative measurements, Clean Steel 3 Conference Proceedings, The Institute of Metals (London), 1987, pp. 60-67 [3] S. Millman, Clean steel Basic features and operating practices, IISI Study on Clean Steel, International Iron and Steel Institute, Belgium, 2004, pp. 8-10 [4] D.M. Mainy, J.P. Nectoux and R. Blondeau, Contribution of computer-aided quantitative microprobe analysis to determination of nonmetallic inclusions in steels, Clean Steel 3 Conference Proceedings, The Institute of Metals (London), 1987, pp. 7884

CHAPTER TWO: LITERATURE REVIEW

Most non-metallic inclusions present in steel have detrimental effects on properties, which will lead to poor formability of the product as well as problems associated with fatigue life. In addition to improved formability, cleaner steel also benefits the coating and corrosion resistant properties. Cleanliness requirements for steel products (Table 2-1) are often measured in total oxygen (T[O]), and maximum particle size (d). Table 2-1: Cleanliness requirements for steel products[1] Product Automotive sheet Drawn and ironed cans Lead frame for LSI Shadow mask for CRT Tire cord Ball bearings Line pipe Cleanliness T[O] < 20ppm d < 100m T[O] < 20ppm d < 20m d < 5m d < 5m T[O] < 15ppm d < 20m non-plastic inclusions T[O] < 10ppm d < 15 m T[O] < 30ppm d < 100m oxide shape Sour gas service Crack prevention during hot-rolling Crack prevention in punch forming Prevention of photo etching Prevention of rupture in wire drawing Increased fatigue life Notes Ultra deep drawing

2.1 Melting and Casting Operations The melting and casting operations, shown in Figure 2-1, are most crucial to cleanliness of steel throughout the steelmaking process. Charge materials include steel scrap, limestone, and metallurgical coke fed into an electric arc furnace, where the melting operation takes place. Once molten, decarburization is then carried out by injecting 4

oxygen into the steel melt; lowering carbon content to the desired level governed by the specific steel grade. The molten decarburized steel is then tapped into a ladle, which is transported to a continuous casting station. Within the ladle vessel, trim alloying elements and deoxidizers such as ferromanganese and ferrosilicon are added to the steel melt in order to remove excessive oxygen carried over from the decarburization process. Manganese and silicon form stable oxides with dissolved oxygen in the steel melt, where most oxide particles are removed by floatation, assisted by inert gas stirring and collection at the slag layer. However, the complete removal of oxide particles cannot be done within reasonable amount of time. The remaining oxide particles exist as inclusions in solid steel. These inclusions are often classified indigenous in origin (Section 2.4.2).

Figure 2-1: Schematic of melting and casting operations in steelmaking[2] Another source of inclusions may arise from oxidation of steel during transfer between ladle to tundish, and tundish to mold. If the stream of previously deoxidized steel is allowed to come in contact with oxygen-containing atmosphere, the dissolved deoxidizers and some alloying elements will readily form oxide particles which have less opportunity to be removed prior to casting and are likely to remain as inclusions. This process is also known as reoxidation. Inclusions of this origin are often classified as exogenous inclusions (Section 2.4.2). Implementing refractory/inert gas shrouding

between ladle and tundish and submerged entry nozzles between tundish and mold can minimize reoxidation.

2.2 Steel Deoxidation Maximum solubility of oxygen in liquid iron at the eutectic of 1527C is about 0.16%.[3] The oxygen solubility in solid iron, at temperature slightly below its melting point, approaches zero. Upon solidification, majority of dissolved oxygen will precipitate as FeO inclusions. In steel, the presence of alloying elements such as carbon can influence the dissolved oxygen content. Equation 2-1 describes carbon-oxygen relationship in iron up to 0.6% carbon. [wt%C] [wt%O] = ~0.0023 (2-1)

In order to prevent blowhole (carbon monoxide gas) formation, porous cast product, or precipitation of FeO inclusions in sizeable quantities, liquid steel must be deoxidized prior to casting.

2.2.1 Thermodynamics of deoxidation The role of deoxidation process is to lower the oxygen content in liquid steel. Deoxidation is commonly carried out by additions of elements having greater affinity for oxygen than iron, this method is also known as precipitation deoxidation. The oxygen affinity of various elements can be compared with free energy of oxide formation. Figure 2-2 gives a plot of curves for common elements found in steelmaking. While elements having free energy of oxide formation lower than FeO are potential candidates as deoxidizers, it is also important to consider that activity of these elements in solution with liquid steel deviates from that of the pure elements. Figure 2-3 depicts the deoxidizing power of various elements at 1600C.

Figure 2-2: Free energy of formation for various oxides. Dash-dot line indicates equal oxygen pressure in unit of atmosphere[4]

Figure 2-3: Deoxidizing power of various elements at 1600C[5] 7

2.2.2 Single component deoxidation Four cost-effective deoxidizers are carbon, manganese, silicon, and aluminum. Carbon is often considered an effective deoxidation element, forming gaseous deoxidation products. Carbon deoxidation does not generate inclusions and therefore will not be discussed further, however, during the casting process, carbon in liquid steel may reduce oxide inclusions resulting in gas formation and pinhole porosity.[6] A general deoxidation reaction can be described using Equation 2-2, where x and y are stoichiometric terms, M is the dissolved deoxidizer, O is oxygen. x[M]steel + y[O]steel = (MxOy) Manganese deoxidation Manganese, in pure form, is rarely utilized as a deoxidizer. Mn is often introduced to steel in the form of low C or high C ferroalloy. Mn and Fe will both participate in the deoxidation reaction forming MnO-FeO product in liquid or solid solutions. A detailed study by Lismer and Pickering[7] has revealed that Mn deoxidation products are typically small and homogeneously distributed in the steel and the morphology of this inclusion type is mostly influenced by the MnO-FeO ratio. For inclusions with MnO content of up to 30%, the morphology was globular single-phase or sometimes dual-phase spheres. These inclusions rich in FeO had solidified after the matrix steel was solid. On the other hand, for steel containing more than 0.7%Mn, it was found that the deoxidation products are mostly pure MnO. Nearly pure MnO inclusions, having higher melting temperature than steel, would solidify before steel, and therefore are characterized by a dendritic structure.[6] The manganese deoxidation reaction, [Mn] + [O] = (MnO) (s) (2-3) (2-2)

and corresponding equilibrium constant equation,

K MnO =

a MnO [% Mn][%O ]
12440 5.33 T

(2-4)

log K Mn O = For

(2-5)

aMnO = 1, the value of the equilibrium constant for manganese deoxidation is

KMn-O = [%Mn][%O] = 4.88 x 10-2 at 1600C (2-6)

Silicon deoxidation It can be seen from Figure 2-3, silicon has a much-improved deoxidizing power compared with manganese. Deoxidation with pure silicon will yield either liquid iron silicates or solid silicon oxide as reaction products at steelmaking temperature. Iron silicate inclusions, like many other silicates, are usually glassy in appearance and globular in morphology. Silicon oxides within steel exist in several modifications as a result of various possible spatial arrangements of the SiO2 tetrahedra molecules. Low quartz, high-quartz, tridymite, and cristobalite are among the common modifications[6]; where tridymite and cristobalite are high temperature modifications of silica. Due to similar structures, low quartz-high quartz transformation as well as tridymite-cristobalite transformation are fast and can be easily reversed. However, the transformation between quartz and tridymite or cristobalite is a much slower process as the energy associated with breaking the tetrahedral bonds are greater. The given reaction time and temperature during ladle treatment are inadequate for the transformation of quartz to tridymite or cristobalite to reach completion. On the contrary, tridymite and cristobalite, often formed as deoxidation product, do not transform to quartz within the time-frame of subsequent cooling and casting of steel. Therefore, the type of modification and composition can be utilized as indicators for assessing silica inclusions origin.

The silicon deoxidation reaction, [Si] + 2[O] = SiO2 (s) and corresponding equilibrium constant equation, (2-7)

K Si O =

a SiO2 [% Si ][%O ]2
30000 11.5 T

(2-8)

log K Si O =

(2-9)

For

aSiO2 = 1, the value of the equilibrium constant for silicon deoxidation is

KSi-O = [%Si][%O]2 = 2.26 x 10-5 at 1600C (2-10)

Aluminum deoxidation From Figure 2-3, it is clear that Aluminum is one of the most effective deoxidizers used for steel deoxidation. In aluminum deoxidized steel, there are generally two species of deoxidation products: solid hercynite (FeO-Al2O3 spinel) and solid corundum (Al2O3, modification). Among the two deoxidation products, corundum is the dominant species found in steel. Corundum phase is characterized by having unique faceted shapes and relative smaller diameter as single particles. It has been reported by Rege et al[8] that Al2O3, during deoxidation, follows dendritic growth pattern as shown in Figure 2-4. For steels deoxidized solely with aluminum, -Al2O3 products are formed; clusters of these particles tend to remain as inclusions in steel. Corundum inclusions, usually having the particle size of 1 to 5 m, have a tendency to agglomerate upon colliding with one another in order to lower the overall contact area with molten steel and therefore effectively stabilize the entire unit by minimizing the surface energy.[6]

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Figure 2-4: a) As-polished (2-dimensional) steel sample showing Al2O3 dendrite b) Partial slime extracted (3-dimensional) steel sample showing the same Al2O3 dendrite[1] Solid deoxidation products are often associated with nozzle clogging during casting of liquid steel. This phenomenon is mainly caused by solid alumina inclusions having high contact angles with liquid steel; therefore, alumina inclusions will readily anchor onto refractory surfaces followed by subsequent agglomeration of inclusions. Indigenous inclusions from aluminum deoxidation may take on different morphology depending on the generation mechanism. There are generally three Al2O3 inclusion generation processes: I. Nucleation by super-saturation: Al2O3 inclusions nucleate homogeneously in the steel bath as a result of supersaturation. The resulting inclusions are finely dispersed corundum clusters[6] II. Nucleation and growth on existing nuclei: The existing nuclei can be both indigenous and exogenous in nature. Manganese and silicon deoxidation products as well as emulsified furnace slag and eroded refractories can serve as low-energy sites for Al2O3 inclusions to nucleate without reaching super-saturation in the bath. III. Reaction between aluminum metal and oxygen: Excess aluminum addition or poor homogenization of the bath can lead to local high concentration of aluminum metal reacting with dissolved oxygen. Reactions that

11

occur under localized superheat may reach the melting point of Al2O3; therefore the products are partly molten Al2O3 inclusions sometimes having glassy appearance. The aluminum deoxidation reaction, 2[Al] + 3[O] = Al2O3 (s) and corresponding equilibrium constant equation, (2-11)

K Al O =

a Al2O3 [% Al ]2 [%O ]3
62780 20.5 T

(2-12)

log K Al O = For

(2-13)

a Al 2 O3 = 1, the value of the equilibrium constant for aluminum deoxidation is

KAl-O = [%Al]2[%O]3 = 9.58 x 10-14 at 1600C (2-14)

2.2.3 Multi-component deoxidation

In conventional ladle deoxidation, a combination of deoxidizers are utilized to achieve improved deoxidation result, giving much lower residual oxygen in the bath. It is a common practice to perform partial deoxidation while filling the tap ladle followed by final killing of steel with aluminum at the ladle furnace station. This practice has many advantages: (1) promotes the formation of low-melting-point deoxidation products with ease of removal from the melt; (2) improves the solubility of elements having relative high vapor pressure such as calcium and magnesium; (3) minimizes nitrogen pick-up during furnace tapping[4].

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Silicon-manganese partial deoxidation

Figure 2-5: Equilibrium relations for manganese-silicon deoxidation of steel at various temperatures[3] The practice of tap ladle deoxidation can effectively improve the extent of deoxidation and at the same time minimize aluminum deoxidizer additions. Two general types of deoxidation products may result from Si-Mn deoxidation: solid silica and liquid manganese silicate at the steelmaking temperature. Under the influence of increasing manganese content, the activity of silica is lowered. As the activity of silica decreases, deoxidation products deviate from pure silica to molten manganese silicate. It was suggested by Turkdogan[3] that there exist critical ratios of [%Si]/[%Mn]2 at a given temperature, which govern the type of deoxidation products formed. As shown in Figure 2-5, for steel compositions left of the curve, the deoxidation products will be solid silica which indicates the absence of manganese participation in the reaction. On the other hand, for liquid steel containing higher manganese content (right of the curve) the primary deoxidation products are likely to be liquid manganese silicate.

13

The equilibrium reaction governing Mn/Si deoxidation, [Si] + 2MnO = 2[Mn] + SiO2 and corresponding equilibrium constant equation, (2-15)

K Mn Si =

[% Mn]2 a SiO2 [% Si ] a MnO

1510 + 1.27 T
2

(2-16)

log K Mn Si =

(2-17)

The Mn/Si deoxidation products are typically found to be globular and glassy in appearance along with silica or rhodonite precipitation within the matrix of manganese silicate. To facilitate the removal of deoxidation products, manganese is added as an inclusion modifier yield liquid manganese silicates for improved coalescence and flotation to the slag layer. Manganese-silicon-aluminum deoxidation In modern practice, it is common to charge deoxidizers into the tapping ladle during ladle filling. The charge deoxidizers often consist of all three deoxidizers; manganese and silicon in the form of ferromanganese, ferrosilicon, or silicomanganese, as well as aluminum. The phases of resulting deoxidation products depend heavily on steel chemistry and reaction temperature as illustrated in Figure 2-6. In the absence of manganese, only solid phases such as silica, alumina and mullite are possible. On the other hand, with manganese participating in steel deoxidation, the fourth phase - liquid manganese silicate becomes stable; the stability range of liquid manganese silicate also increases with increasing manganese content.

14

Figure 2-6: The effect of manganese content on stability of oxide phases resulting from steel deoxidation at 1550C (m: mullite; l: liquid manganese silicate)[9] Liquid silicates, in this deoxidation process, are characterized by an aluminum-rich core and a shell of gradual increase in MnO-SiO2 content towards steel-inclusion interface. The outer glassy MnO-Al2O3-SiO2 matrix, in metastable condition, was often found to precipitate phases such as mullite, galaxite, and corundum lathes upon cooling in solid state. These precipitates can nucleate easily on small steel particles or solidified slag droplets within the inclusion. Calcium modification From Figure 2-2, it can be seen that calcium has a strong affinity to oxygen and could potentially be utilized as steel deoxidizer. The challenge, however, lies in the following properties of calcium: low boiling point (1439C), limited solubility in steel (0.032% Ca at 1600C), and high vapor pressure at 1600C (1.81atm).[10] Due to these reasons, it is rather difficult to introduce calcium to molten steel in its metallic form, and it is usually added as various iron-containing Ca-Si alloys. The primary deoxidation products are therefore calcium silicates, which may also contain other oxides. When combinations of Ca and Al or Mn/Si deoxidation are carried out, the primary deoxidation products can be modified to oxides with lower activity and hence improve the removal of dissolved oxygen. By converting the solid alumina inclusions to liquid calcium aluminates, the 15

extent of deoxidation can be improved from 8-10ppm O to 1ppm O in Al-killed steel (0.05% Al).[9] With a CaO:Al2O3 ratio of 12:7, calcium treated Al2O3 can reach a melting point of 1360C at the CaO-Al2O3 eutectic (Figure 2-7) and therefore exists in the liquid state at steelmaking temperatures. Moreover, there exist five modifications of calcium aluminates as indicated in Figure 2-7; 12CaO7Al2O3, 3CaOAl2O3 and CaOAl2O3 are liquid, while CaO2Al2O3 and CaO6Al2O3 are solid at steelmaking temperatures.

Figure 2-7: CaO-Al2O3 equilibrium phase diagram[10] Instead of agglomerating, in alumina inclusions, liquid calcium aluminates will coalesce upon contact due to better wetting with liquid steel and will not easily attach onto refractory surfaces. Hence, solid deoxidation products can also be calcium treated so that the steel casting process is clogging-free.

16

2.3 Manganese Oxide Silicon Oxide Aluminum Oxide System

The MnO-SiO2-Al2O3 system effectively covers most of relevant inclusion phases that result from combination of Mn, Si, and Al deoxidation. Figure 2-8 summarizes many complex inclusions having compositions made up of various SiO2, MnO, and Al2O3 primary oxide contents. It is important to note that each inclusion species will have its own homogeneity range in addition to stoichiometric compositions listed in Table 2-2.

Figure 2-8: Schematic representation of MnO-SiO2-Al2O3 ternary phase diagram[6] Other inclusion systems such as FeO-SiO2-Al2O3 and MnO-SiO2-Cr2O3 share many similarities with the MnO-SiO2-Al2O3 system. Considerable numbers of MnO-SiO2Al2O3 inclusion phases exist with complete or part substitution of MnO with FeO due to wide range of solid solubility; with the exception of FeO-SiO2 (counterpart to MnOSiO2), which has yet to be reported as an inclusion phase in the literature. According to Figure 2-2, manganese has a stronger affinity for oxygen than iron and therefore it is also common to find MnO among inclusions belonging to the FeO-SiO2-Al2O3 system. On the 17

other hand, Al2O3 and Cr2O3 are interchangeable at elevated temperatures due to their structural resemblance. Corresponding inclusion phases were often reported in both MnO-SiO2-Al2O3 and MnO-SiO2-Cr2O3 with notable difference in the absence of ternary phases in the MnO-SiO2-Cr2O3 system.[5] Corresponding phases relating to MnO-SiO2Al2O3, FeO-SiO2-Al2O3, and MnO-SiO2-Cr2O3 systems are summarized in Table 2-3. Table 2-2: Stoichiometric composition of reported inclusion phases in Figure 2-8[6] Mineral classification Corundum Cristobalite Tridymite Quartz Manganosite Galaxite Mullite Rhodonite Tephroite Spessartite Chemical formula Al2O3 SiO2 SiO2 SiO2 MnO MnO Al2O3 3Al2O3 2SiO2 MnO SiO2 2MnO SiO2 3MnO Al2O3
3SiO2

Stoichiometric composition (wt%) MnO ----100 41 -54 70 43 SiO2 -100 100 100 --28 46 30 36 Al2O3 100 ----59 72 --21

Mn-Anorthite

MnO Al2O3
2SiO2

24

41

35

Mn-Cordierite

2MnO 2Al2O3
5SiO2

22

46

32

18

Table 2-3: Inclusion phases found in MnO-SiO2-Al2O3, FeO-SiO2-Al2O3, and MnO-SiO2Cr2O3 systems[6]

MnO-SiO2-Al2O3
Mineral classification Corundum Cristobalite Tridymite Quartz Manganosite Galaxite Chemical formula Al2O3 SiO2 SiO2 SiO2 MnO MnO Al2O3 3Al2O3
2SiO2

FeO-SiO2-Al2O3
Mineral classification Corundum Cristobalite Tridymite Quartz Wstite Hercynite Chemical formula Al2O3 SiO2 SiO2 SiO2 FeO MnO Al2O3 3Al2O3
2SiO2

MnO-SiO2-Cr2O3
Mineral classification Escolaite Cristobalite Tridymite Quartz Manganosite Chromium Galaxite -Rhodonite Tephroite Chemical formula Cr2O3 SiO2 SiO2 SiO2 MnO MnO Cr2O3

Mullite Rhodonite Tephroite

Mullite -Fayalite

-MnO SiO2 2MnO SiO2

MnO SiO2 2MnO SiO2 3MnO

-2FeO SiO2 3FeO

Spessartite

Al2O3
3SiO2

Almandine

Al2O3
3SiO2

--

--

2.4 Classification of Non-Metallic Inclusions

2.4.1 Based on inclusion chemistry and composition

Oxides In general, oxide inclusions can be classified into: Single oxides; some common examples: FeO, Fe2O3, MnO, SiO2, Al2O3, Cr2O3, TiO2 19

Complex oxides, often takes the general form of AOB2O3, where metal A has +2 oxidation number and metal B has +3 oxidation number. Some common examples are FeOAl2O3, MnOAl2O3, MgOAl2O3, FeOCr2O3, MnOCr2O3

Complex oxide inclusions are sometimes known as spinel type (MgOAl2O3) inclusions for their similarity in structures. Spinel type inclusions are characterized by faceted structure and high melting temperature, usually higher than steelmaking temperature of 1873K. Spinel inclusions are especially harmful during steel processing as they do not deform during hot rolling and often cause poor surface finish. Calcium aluminate (CaOAl2O3) type inclusions are also considered complex oxide inclusions. Calcium and barium, have +2 oxidation number, but do not form spinel structures due to their relatively large ionic radius. With common calcium treatment practice, the usual Al2O3 inclusions are modified to calcium aluminates, which effectively lower the melting temperature of inclusions from 2293K to around 1700K. Sulphides Sulphide inclusions are important to consider since it is common to have steel with oxygen content less than 0.02% while having sulphur content at around 0.03%. Liquid steel has a high solubility of sulphur where solid steel usually has significantly lower sulphur solubility. As liquid steel cools, sulphur segregates and forms FeS with melting point of 1460K. FeS often causes embrittlement of steel during heat treatment. Therefore it has become a common practice to add sufficient amount of Mn, due to manganeses stronger affinity for sulphur, to form MnS (Tm = 1870K). Types of sulphide inclusions will also depend on manganese to sulphur ratio. Examples of common sulphide inclusions include MnS, FeS, (Mn, Fe)S and CaS. The sulphur affinity of various elements can be compared with free energy of sulphide formation. Figure 2-9 gives a plot of curves for common elements found in steelmaking.

20

Figure 2-9: Free energy of formation for various sulphides. Dash-dot line indicates equal sulphur pressure in unit of atmosphere[4] Two morphologies are frequently observed: Globular: Both simple sulphides and oxysulphides, where the latter consists of sulphides and oxides coexisting in one inclusion. This type of morphology is generally present in silicon killed or semi-killed steel using aluminum, titanium, or calcium. Nitrides In the presence of elements having high affinity for nitrogen, nitrides such as AlN, TiN, ZrN, VN, BN, etc. can form as a result of molten steel contacting with air atmosphere during unprotected vessel transfer. Like carbides, nitride inclusion contents in steel are significantly less than that of oxides and sulphides. Faceted: Often appears in steel heavily deoxidized with aluminum.

21

2.4.2 Based on inclusion formation mechanism

There are generally two sources of inclusions in steel: exogenous, indigenous. Exogenous inclusions, usually larger in size, are results of reoxidation, slag entrainment and refractory erosion. Although exogenous inclusions are generally more harmful than indigenous inclusions, simple detection methods (due to larger size) as well as fewer occurrences have reduced the concern for exogenous inclusions significantly. In addition, with careful control of stirring and flowrate monitoring, the amount of exogenous inclusions can be minimized. Indigenous inclusions, such as deoxidation products, are generated by chemical reactions between dissolved species in the steel bath and are generally smaller in size. Deoxidation products originate from the reaction between dissolved oxygen and added deoxidants and can be both solid and liquid at steelmaking temperatures. The presence of a few large indigenous inclusions has a strong effect on the properties of steel products. Indigenous inclusions often go through a series of transformations as the steel cools from 1600C to room temperature. While trying to maintain equilibrium with the surroundings, inclusions may be undercooled during some steps of the treatment and result in amorphous phases, or solidify and take the form of supersaturated solid solution. Indigenous inclusions can therefore be categorized into formation steps, as summarized below: I. Primary inclusions: generated during deoxidation reaction II. Secondary inclusions: generated due to equilibrium shift as temperature decreases during vessel transfer, such as tapping and teeming operations III. Tertiary inclusions: generated during the process of solidification, usually characterized by rapid cooling IV. Quaternary inclusions: generated during solid state phase transformation, which causes changes in solubility limits of various constituents 22

2.5 References

[1] L. Zhang and B.G. Thomas, State of the Art in Evaluation and Control of Steel Cleanliness Review, ISIJ International, 2003, vol. 43, no. 3, pp. 271291 [2] http://www.matter.org.uk/steelmatter/casting/5_1_5_2_7.htm, Entrapment of nonmetallic inclusions, Corus Corp. and Matter, date accessed: June 16, 2009 [3] E.T. Turkdogan, Fundamentals of Steelmaking, The Institute of Materials (London), 1996, pp. 111-113 [4] A. Muan and E.F. Osborn, Phase Equilibria Among Oxides in Steelmaking, AddisonWesley, Reading, Mass., USA, 1965, p. 4 [5] H.A. Sloman and E.L. Evans, JISI, 1951, vol. 169, pp. 145-152 [6] R. Kiessling and N. Lange, Non-Metallic Inclusions in Steel, The Institute of Materials (London), 1978, vol. 2, pp. 13-50 [7] R.E. Lismer and F.B. Pickering: JISI, 1952, vol. 170, pp. 48-50 [8] R.A. Rege, E.S. Szekeres and W.D. Forgeng, "Three-Dimensional View of Alumina Clusters in Aluminum-Killed Low-Carbon Steel", Met. Trans., AIME, 1970, vol. 1, no. 9, pp. 2652-2653 [9] S. Millman, Clean steel Basic features and operating practices, IISI Study on Clean Steel, International Iron and Steel Institute, Belgium, 2004, pp. 39-60 [10] T. Ototani, Calcium Clean Steel, Springer-Verlag, New York, 1986, pp. 2-9

23

CHAPTER THREE: EXPERIMENTAL ASPECTS

3.1 Overview

The main purpose of this study was to characterize the non-metallic inclusions found in high strength low alloy steel for structural applications and to track the development of inclusions throughout the melting and casting operations. To do this, the experimental approach was divided into two parts: qualitative and quantitative aspects. Qualitative assessment involves inclusion morphology examination and inclusion type determination by combining electrolytic dissolution technique for sample preparation and analytical techniques such as scanning electron microscope (SEM) and energy dispersive x-ray spectroscopy (EDS). Quantitative assessment involves the inclusion detection and size determination, which ultimately leads to the construction of inclusion particle size distribution by image analysis method. The experimental approaches are summarized in Figure 3-1.

Inclusion Analysis
Sample preparation (grinding and polishing of specimen)

Qualitative Assessment
Dissolution of matrix by SPEED method Inclusion species and morphology study by SEM and EDS

Quantitative Assessment
Image acquisition by SEM Backscattered electron mode Inclusion counting by image analysis

Figure 3-1: Flow chart of the scheme of experiments

24

3.1.1 Sample preparation

Steel grades involved in this study are ASTM 529 grade 50 and ASTM 1018S High Strength Low Alloy steels for structural applications, both of which are silicon-killed and provided by Gerdau Ameristeel at Whitby, Ontario. Two metal samples were taken from each stage of the melting and casting operations. The chemical analysis results corresponding to each sampling location are summarized in Table 3-1. The sampling locations include furnace tap, ladle, ladle tap, tundish and billet as depicted in Figure 3-2. Table 3-1: Specimen chemical composition

Grade

description Ladle tap Tundish Billet

529 (50) Furnace tap

C 0.1 0.16 0.17 0.18

Mn 0.64 0.68 0.74 0.8

P 0.01 0.01 0.01 0.01

S 0.05 0.04 0.03 0.03

Si 0.13 0.19 0.17 0.18

Cu 0.31 0.31 0.33 0.33

Ni 0.1 0.1 0.09 0.1

Cr 0.04 0.04 0.05 0.05

C 1018S Furnace tap 0.05 Ladle tap Tundish Billet 0.16 0.167 0.160

Grade description

Mn P S 0.67 0.008 0.035 0.66 0.008 0.025 0.68 0.009 0.028 0.68 0.010 0.027

Si 0.16 0.17 0.19 0.18

Cu Ni Cr 0.20 0.051 0.049 0.19 0.046 0.060 0.19 0.054 0.060 0.19 0.054 0.056

Figure 3-2: Sampling locations

25

Specimens were ground to grit 1200 on wet silicon carbide papers followed by 1 m alumina suspended solution and then 0.3 m alumina suspended solution for final polishing on velvet cloth. It is important to note that contamination of abrasive particles from either silicon carbide paper or alumina-polishing agent may take place during sample preparation.

3.2 Qualitative Assessment

Both inclusion morphology and inclusion species have a dominant effect on steel properties. An electrolytic dissolution technique was used to selectively dissolve the steel matrix, thereby allowing examination of inclusion morphology by SEM and subsequent inclusion type determination with EDS.
3.2.1 Inclusion morphology examination (SPEED method[1])

The Selective Potentiostatic Etching by Electrolytic Dissolution (SPEED) method is a selective etching technique developed for in-situ observation and analysis of inclusions, precipitates and grain orientations in steel samples. By varying control parameters such as the composition of electrolyte, applied potential, current density and temperature, the matrix material can be selectively dissolved into the electrolytic solution and leave behind the phases of interest, such as inclusions and precipitates. A schematic of the SPEED apparatus is shown in Figure 3-3.

26

Calomel reference electrode Cathode (Pt) Electrolyte Anode (sample) Filter clamp Filter Power control unit Draining vessel

Figure 3-3: Schematic of SPEED apparatus [1] In this method, non-aqueous solutions are employed as electrolyte in which the samples are etched at predetermined constant electrical potential. The electrolyte used consists of 10% acetylacetone [CH3COCH2COCH3] 1% tetramethylammonium chloride [(CH3)4NCl] balance methyl alcohol [CH3OH].[1] The optimum applied electrical potential, which varies with different materials, was determined by conducting a preliminary etching procedure on a sample material. The preliminary etching procedure starts with applying 500 mV to the system and increases by increments of 50 mV every 5 minutes until 800 mV applied potential is reached. The measured current was recorded following each applied potential change. Gathered data were used to construct a currentpotential curve, also known as an anode polarization curve, where the optimum applied potential at 400 mV was indicated by the first peak on the curve, shown in Figure 3-4. Etching of samples reported in this thesis was performed at 400 mV for 20 minutes.

27

Optimum potential

Figure 3-4 Anode polarization curve Upon completion of the etching process, the passive inclusion phase can either be found on the matrix or in the electrolytic solution as a result of extraction. Extracted inclusions and etched samples were analyzed and observed using analytical methods such as SEM/EDS. SEM images, taken using acceleration voltage of 20kV, provide threedimensional views and yield information on the shape and morphology of inclusions, which is rather difficult to obtain from conventional polished samples.

3.2.2 Inclusion species analysis

The chemical composition of different observed inclusions was determined by EDS analysis from the same SEM where the images were taken. As oxygen content cannot be accurately measured using EDS technique, the analysis of inclusion composition faces certain challenge especially when oxide inclusions are in majority. However, the said difficulty is not too severe knowing that no other light elements are present in comparable concentrations at the same time. Calculation of inclusion chemistry was made possible with general knowledge about inclusion types as well as relevant elemental valencies

28

such as Al, Si, Mn, Fe and other metals. It is widely accepted that analysis having total oxides within 100 5% is satisfactory.[2] Inclusion types reported in this thesis are mainly classified based on respective EDS spectra and morphologies. Therefore chemical formulae, instead of common mineral classification, are utilized in inclusion type description. However, inclusions with characteristic appearances, which can be easily identified, will also be given a mineral classification. A more precise classification of non-metallic inclusions involves the determination of phases as each chemical formula may include different phases, which give rise to different properties and different formation conditions are often required. Kiessling and Lange[2] gave detailed reports on inclusion phases determined using electron probe analysis.

3.3 Quantitative Assessment

A complete assessment of steel cleanliness not only consists of qualitative information, but also quantitative information such as inclusion length, inclusion width, number of inclusion per unit area, volume fraction, mean free path, etc. Using as-polished metal samples, quantitative assessment involves a combination of a microscopic technique to provide images of the sample surface (image acquisition) and an image analysis system to accurately measure the inclusion size.

3.3.1 Image acquisition

Image acquisition is a crucial part in the process of quantitative analysis. The ideal technique for providing images of the sample surface must offer accurate representation of inclusion distribution. Analytical instruments involved in this research project consist of the following: 1. Light optical microscope 2. Laser confocal microscope 29

3. Scanning electron microscope Light optical microscope: Prior to the advent of electron microscopy, light-optical microscopy was used to quantify and characterize inclusions based on morphology. The best-possible spatial resolution of a light-optical microscope, which is approximately 0.3m , is limited by the fixed
wavelength of light ( 0.5m ).[3] As the magnification increases, the light intensity decreases, which results in darker image. Therefore it becomes rather difficult to utilize the best-possible resolution of light in a conventional light-optical microscope. Laser confocal microscope: The laser confocal microscope (LCM) distinguishes itself from conventional optical microscope and SEM in the following way: Laser confocal microscope is able to provide height information accurate to 0.01 m. Once the height information is obtained, quantitative surface area and volume measurement can then be calculated using the operating software. This technique is especially important for particle analysis of metallurgical samples such as isolated inclusions, etc. With DIC (differential interference contrast), laser confocal microscope provides 3dimensional images comparable to that of SEM, but without the issues of charging in non-metallic areas of interest such as inclusions. LCM utilizes blue laser as the transmitting medium, which has a wavelength of 473nm. Therefore, when compared to light optical microscope, LCM offers a slightly improved lateral spatial resolution at approximately 200nm. Scanning electron microscope: SEM and EDS are among the most employed methods of inclusion investigation mainly due to the following advantages: high resolution, high sensitivity, quantifiability, minimal sample preparation and ease of operation. The secondary electron mode of a SEM provides an improved spatial resolution of 5~20 nm.[3]

30

The three modes used are secondary electron (SE), backscattered electron (BSE) and EDS modes. Using the SE mode, the images formed are topographical representations of the specimen. Since secondary electrons have a very small escape depth, the signals received will reflect the surface structures of the specimen. However, using SE mode to locate inclusions in a polished sample, given the topography of the specimen is flat, will be rather difficult when inclusion size is small. The BSE mode, on the other hand, utilizes backscattered electrons to create images showing elemental contrast, thereby revealing the locations of non-ferrous inclusions in the ferrous matrix. BSE images are also able to provide information on the homogeneity of inclusions. In the current investigation, SE mode was used to image inclusions on polished and SPEED etched surfaces for inclusion morphology study. Inclusion type determination was performed by EDS mode simultaneously. For inclusion quantification, the BSE mode was used in conjunction with image analysis software.

3.3.2 Image analysis

Detection and discrimination of inclusions utilize the difference in gray level intensity between each inclusion species and the unetched matrix steel.[4] Measurements are made based on counting the number of picture point elements (termed pixels) that satisfy the user-defined gray level threshold. The dimension of each image pixel is dependent on both microscope magnification setting and image resolution. The images for the purpose of quantitative analysis in this study are taken with the following parameters: Magnification: 100X Image resolution: 512 X 676 pixel Dimension of each pixel: 1.742 m/pixel Figure 3-5 shows images taken of the same sample area, using four image acquisition techniques: optical microscopy, laser confocal microscopy, SEM (SE mode) and SEM (BSE mode). Figure 3-5 (a)-(b) are examples where surface defects such as voids and gas 31

holes due to solidification shrinkage, or limited hot ductility may be detected as oxide inclusions in optical microscopy and LCM images; because their gray level range is comparable to that of oxides.[4] Other surface defects may also result from improper polishing techniques, creating excessive relief pits, voids and deep scratches. Figure 3-5 (c) (SE mode), although reduced in number of surface defects, proved to be difficult in image analysis processing due to lack of contrast between inclusion and matrix steel.

(a)
Scratch

(b)
Voids

MnS inclusions

(c)

(d)

Figure 3-5: Images acquired using (a) optical microscopy, (b) laser confocal microscopy, (c) SEM (secondary electron mode) and (d) SEM (backscattered electron mode) The presence of defects in acquired images shown in Figure 3-5 (a) and (b) can greatly affect the reliability of subsequent inclusion detection and measurement represented in

32

Figure 3-6 (a), where the voids and scratches were identified as inclusions by the image analysis software. However, complete elimination or minimization of these defects at the image acquisition stage can be achieved using SEM under BSE imaging mode as shown in Figure 3-5 (d) and its respective image analysis result in Figure 3-6 (b). Thus, SEMBSE is chosen as the most suitable image acquisition technique for the quantitative analysis of inclusions.

(a)

(b)

Figure 3-6: Photograph processed by image analysis showing detected area as inclusions (a) laser confocal microscopy, (b) SEM (backscattered electron mode) Two specimens were studied for each steelmaking operation, where the cleanliness of each operation is indicated by an averaged result. Each specimen has a surveyed area of at least 15mm by 15mm. Within the surveyed area, 40 fields of view were taken as data images for subsequent image analysis. The field areas were aligned contiguously over a rectangular area of 10 X 4 fields. Data images are then compiled and processed using Discover Essentials software. The analysis of an image begins at setting the gray level threshold that corresponds to the inclusions, which are showing as clusters of pixels on the image. The next step is to define the classifications by creating bins that will hold data of various ranges of values. The bins in this investigation are set to hold measurements of inclusion particle size and area fraction. The defined range of each particle size bin are: 0-10, 10-30, >30 in micrometer units. Lastly, prior to identification,

33

specific recognition parameters are imperative for the software to correctly identify an inclusion based on the geometry. Parameters such as diameter inner maximum, diameter inner minimum, area, aspect ratio, number of edges, etc. have optional upper or lower limit filters to ensure accurate inclusion recognition.

3.4 References

[1] K. Takimoto, I. Taguchi, and R. Matsumoto, Extraction and Determination of Precipitates in Steel by Potentiostatic Electrolysis with Non-aqueous Electrolyte, J. Japan Institute of Metals, 1976, vol. 40, no. 8, pp. 834-838 [2] R. Kiessling and N. Lange, Non-metallic inclusions in steel, The Institute of Materials (London), 1978, pp. 5-10 [3] R. Egerton, Physical Principles of Electron Microscopy: An Introduction to TEM, SEM, and AEM, Springer, New York, 2005, p. 6 [4] ASTM International, E45 Test Methods for Determining the Inclusion Content of Steel, Annual Book of ASTM Standards, ASTM, Philadelphia, USA, 2003, vol. 03

34

CHAPTER FOUR: RESULTS AND DISCUSSION

4.1 Qualitative Assessment

Metal samples from each of the five sampling locations taken from the two steel grades, for a total of 10 samples, were etched by electrolytic dissolution and observed using SEM. A second set of 10 samples, polished and unetched, were also studied using SEM. In this section different oxide and sulphide species are discussed in separate groups, according to chemical composition. Inclusion phases identified in the present work include: Primary oxides: Al2O3 (alumina), SiO2 (silica), MnO (manganosite) Binary oxides: MnO-SiO2 (rhodonite), MnO-Al2O3 (galaxite), CaO-Al2O3 (calcium aluminate), CaO-SiO2 (calcium silicate) Ternary oxides: MnO-Al2O3-SiO3 (calcium aluminosilicate) Sulphides: MnS (manganese sulphide) type I

Different modifications of the same inclusion species are also presented in the current investigation. A modification of an inclusion species, very often, shares similar chemical composition with other members of the same species while possessing distinguishable morphology. However, calcia-rich inclusion systems sometimes share similar optical properties between the various phase modifications and therefore differentiation among them can be challenging.

4.1.1 Al2O3 (Alumina)

Corundum (-Al2O3), shown in Figure 4-1, is a common inclusion phase found in steel as a result of deoxidation and refractory erosion. The main source of indigenous corundum inclusions arises from aluminum deoxidation. However, even when deoxidation is performed by aluminum-free deoxidizers, corundum inclusions can still be found. This is mainly due to trace aluminum impurities present in alloy additions and deoxidizers as well as aluminums extremely low KAl-O = [%Al]2[%O]3 value, which is in the order of 10-14. It can be seen from the EDS spectra that Al2O3 inclusions, whether 35

crystalline or amorphous, are almost pure; containing small amount of other metal oxides including MnO and ferrous oxides. It is also important to keep in mind that, due to electron interaction volume and X-ray generation, Fe signals in EDS spectra can be an artefact reading from the steel matrix. For electron accelerating voltage of 20kV, this phenomenon is much pronounced for target inclusion having particle size less than 2 m.

Al2O3

Figure 4-1: Oxide inclusions found in 1018S ladle sample: alumina

Figure 4-2: Oxide inclusion found in A529 billet sample: alumina dendrites

36

Many of the observed corundum particles are partly held together by Al2O3 dendrites (Figure 4-2) upon collision, forming alumina clusters. It should then be realized that these alumina clusters are 3-dimensional units, as depicted in Figure 4-3, and will grow in dimension as further agglomeration takes place. This Al2O3 inclusion generation behaviour is also referred to as type I nucleation (see Section 2.2.2).

a)

Al2O3

b)

Al2O3

Figure 4-3: Oxide inclusions found in A529 ladle sample: a) alumina and galaxite (G) b) alumina cluster

37

Single-phase glassy alumina inclusions are frequently found to have globular shape as shown in Figure 4-4. Globular morphology was an indication of the alumina inclusion being partly molten when formed; mainly caused by localized superheat and poor homogenization of the bath, as described by type III formation process (see Section 2.2.2). Glassy alumina inclusions are sometimes observed as having plate morphology with 5 m or less in thickness. Figure 4-5 shows alumina laths as an example of such plate morphology in cross-section. Corundum can also be found in multiphase inclusions as a result of type II generation process (see Section 2.2.2). Micrographs in Figure 4-6, showing multiphase oxide inclusions, are examples of corundum nucleation in molten manganese aluminosilicate (Figure 4-6a) and calcium aluminate (Figure 4-6b). It is of importance to note that corundum is microscopically similar to galaxite and spinel inclusions (see Section 4.1.5); in this case, inclusions shown in Figure 4-6 may in fact include galaxite and spinel inclusions. Alumina inclusions found in the current samples bear little resemblance to the faceted morphology reported in the literature. Faceted alumina inclusions are often the result of deoxidation by adding excess aluminum to ensure low residual oxygen in the bath. However, the steel samples in the current investigation were primarily deoxidized by Mn/Si partial deoxidation followed by trim additions of aluminum for final killing. Most of the alumina inclusions examined appear to be spherical on a polished surface (Figure 4-1). The difference in morphology is probably attributed to manganese and silicon reaction with primary corundum during cooling of the liquid steel. The precipitation of MnO and SiO2 may cause a shift in overall inclusion composition and in turn, promote initial crystallization of galaxite phase.

38

Figure 4-4: Glassy Al2O3 (globular) inclusions found in 1018S furnace tap sample

Figure 4-5: Glassy Al2O3 (plate) inclusions found in 1018S ladle sample

39

a) C

b)

M C

Figure 4-6: Oxide inclusions in steel: corundum in a) manganese aluminosilicate matrix [1018S ladle tap sample] b) calcium aluminate matrix [A529 tundish sample]

40

4.1.2 SiO2 (Silica)

Silica inclusions were frequently found throughout silicon-killed steel as indigenous deoxidation products, and exogenous slag entrapment. In this study, three silica modifications have been identified: cristobalite, low quartz and tridymite. Cristobalite is a high temperature modification of silica[1]. Transformation is usually not fast enough during cooling of the steel, and therefore cristobalite often remains metastable at room temperature. It was found, in the current investigation, that cristobalite phase only crystallizes as dendrites within a single- or multi-phase silicate matrix. However, literature[2] has indicated the possibility for cristobalite phase to also be present as inclusion matrix in ferroalloys. Micrographs of polished surface will show these dendrites taking on flower-like shape (Figures 4-7 and 4-9). Unlike other silica modifications, cristobalite phase has extended solid solubility of other metallic oxides. Depending on the species of dissolved oxides present, the inclusions origin and its formation process can be deduced. An example is given in Figure 4-9. The inclusion in Figure 4-9 shows fine and evenly distributed dendrites containing several percent of Al2O3 and MgO, which often serve as an indicator of exogenous origin. Alumina and magnesia particles acted as nucleation sites for cristobalite dendrites. The source of alumina and magnesia in silicon-killed steel is likely from reaction between refractory lining and liquid deoxidation product such as manganese silicate or manganese aluminosilicates. In comparison with Figure 4-7, the large and well-defined dendrites contain 100% SiO2 thus indicating that the inclusion particle is indigenous. Quartz has both low and high temperature modifications, hence the low-quartz and high quartz convention, where transformation often occurs at 573C[1]. As mentioned in Section 2.2.2, the one-way transformation from quartz to cristobalite or tridymite is possible but often incomplete in steelmaking due to inadequate reaction time and temperature. Therefore it is clear that quartz particles (Figure 4-8), which frequently crystallize from molten amorphous silica at steelmaking temperature, are conceivably exogenous in nature. 41

K R

Figure 4-7: Oxide inclusion in A529 billet sample: cristobalite (K) in rhodonite (R)

42

Figure 4-8: Oxide inclusion in A529 billet sample: rhodonite (R), low quartz (Q), tridymite (T) and glassy silica (A) The large inclusion particle shown in Figure 4-8 consists of two distinct components: manganese silicate in the form of rhodonite and silica in the form of low quartz and glassy silica. The intermediate phase, being darker than quartz and lighter than glassy silica, is an example of incomplete transformation of quartz to cristobalite or tridymite during cooling of the steel. In the presence of low quartz and glassy silica, it is reasonable to conclude that the inclusion type shown in Figure 4-8 has an exogenous origin with possible source being silica sand. Moreover, the quartz particle may also act as a preferential site for other particle nucleation. The rhodonite component in Figure 4-8 is probably a result of existing manganese silicate particle growth by dissolution and partial

43

consumption of the quartz component. This observation also holds true for inclusion particle in Figure 4-9, where the glassy silica has been attacked by rhodonite matrix.

Figure 4-9: Oxide inclusion in A529 tundish sample: cristobalite (K) in rhodonite (R) matrix, and glassy silica (A) Other common low quartz inclusion morphologies include cubic and bar as shown in Figures 4-10 and 4-11. It can be seen that the thin and plate-like dark phase, which is characteristic of tridymite, exists on the outer layer of the quartz particle shown in Figure 4-10. However, the exact composition cannot be determined due to limited resolution of the technique used. Follow-up analysis with Auger Electron Spectroscopy will be helpful.

44

T
Figure 4-10: Oxide inclusion in 1018S tundish sample: low quartz (Q) and tridymite (T)

Figure 4-11: Oxide inclusion in 1018S billet sample: low quartz (Q)

45

4.1.3 MnO (Manganosite)

Throughout the investigation, no pure form of manganosite is observed in current steel samples. As a reaction product of a relatively weak deoxidizer, manganosite tends to be reduced by stronger deoxidizers upon formation or simply form solid solution with other oxides, thereby lowering the melting point of the product thus improving the extent of deoxidation. However, it has been repeatedly reported in the literature[2-3] that manganosite exists as an inclusion phase in steel. There exists a wide range of solid solubility between MnO and FeO. It was mentioned in Section 2.2.2 that iron participation in manganese deoxidation gives rise to MnO-FeO as deoxidation products. The mechanism and thermodynamics of formation is given in detail by Turkdogan[4]. Figure 4-12 provides examples of MnO-FeO indigenous inclusions containing about 35% MnO and 65% FeO.

Figure 4-12: Oxide inclusion in A529 billet sample: manganosite 46

4.1.4 MnO-SiO2 (Rhodonite)

Manganese silicate, rhodonite, is a common inclusion phase resulting from Si-Mn deoxidation. By plotting the manganese and silicon contents of steel samples given in Table 3-1 on the deoxidation product stability diagram shown in Figure 2-5, it is clear that molten manganese silicate will likely form as the deoxidation product at 1600C. In the current investigation two morphologies of rhodonite phase were found, single-phase inclusions and the matrix component of a multi-phase inclusion. Rhodonite single-phase inclusions often exhibit a round globular shape on the polished surface, shown in Figures 4-13 and 4-14 (left), and are frequently observed as spherical droplets on a SPEED etched surface, Figure 4-16.

Figure 4-13: Oxide inclusions found in A529 ladle tap sample: rhodonite Liquid manganese silicate has a high solubility of silica at steelmaking temperatures. During subsequent cooling, excess silica in manganese silicate is precipitated as cristobalite while manganese silicate crystallizes as a rhodonite matrix. (Figures 4-7 and 47

4-14, right) Depending on the rate of cooling and length of later heat treatment, the complete transformation of glassy manganese silicate to rhodonite may not be achieved. Single-phase rhodonite inclusions are often considered to be indigenous; however, as illustrated in Section 4.1.2, hints to the origin of rhodonite in multi-phase inclusions lie within the inclusion morphology and the trace elements present. It is common practice to have a high Mn-Si ratio in steel hence it is important to note[1] that the interaction between dissolved manganese in liquid steel and silica in the refractory material is a major source of silicate inclusions such as rhodonite. The composition of the resulting silicate product is also partly dependent on the Mn-Si ratio of the steel.

K R R

Figure 4-14: Oxide inclusions found in A529 billet sample: rhodonite (R) and cristobalite (K) Substitution of MnO by FeO and CaO was observed for rhodonite inclusions. The rhodonite inclusion shown in Figure 4-15 is an example of CaO substitution for MnO. Like type I sulphide inclusions, rhodonite may also undergo plastic deformation forming elongated stringers along the steel rolling direction. (Figure 4-15)

48

Figure 4-15: Oxide inclusions found in A529 billet sample: rhodonite (after rolling)

Figure 4-16: Oxide inclusions found in 1018S ladle sample: rhodonite

49

4.1.5 MnO-Al2O3 (Galaxite)

Galaxite inclusions were often found alongside alumina inclusions as shown in Figure 43. It was observed that the occurrence of galaxite phase increases noticeably from furnace tap samples to billet samples. At the beginning of the melting and casting operations, high aluminum content in the steel may have induced the crystallization of corundum as the primary phase. Addition of silico-manganese during ladle deoxidation resulted in an increase of MnO and SiO2 in the inclusions. This shift in overall composition has improved the stability range of the galaxite phase; consequently, alumina inclusions were dissolved and galaxite phase was precipitated as the steel moves from one processing stage to the next. Inclusions of galaxite phase likely originate from deoxidation and therefore are indigenous in nature. Galaxite (Figure 4-17) and corundum phase are microscopically similar in that they are both faceted and do not deform during hot rolling.

Figure 4-17: Oxide inclusions found in A529 furnace tap sample: galaxite (G)

50

It is of interest to note that there exists a wide homogeneity range for galaxite phase inclusions found in the samples. Galaxite inclusions with MnO content between 30% MnO and 60% MnO were found. Galaxite phase belongs to the spinel family, usually composed of double oxides. These double oxides are structurally similar; therefore, in galaxite inclusions part substitution of manganese with iron(II) and magnesium as well as part substitution of aluminum with iron(III) and chromium was frequently observed. An example is shown in Figure 4-18, where chromium partly substituted for aluminum, forming chromium galaxite phase. Like other spinel inclusions, chromium galaxite also had a wide homogeneity range: between 15% MnO and 32% MnO.[1]

Cr G

Figure 4-18: Oxide inclusions found in 1018S ladle tap sample: galaxite (G) and chromium galaxite (Cr G) Galaxite phase can also be found in multi-phase inclusions, often as precipitates. Example of such an inclusion is shown in Figure 4-20, where calcium aluminate is the

51

matrix phase. In addition, literature[1] has reported the observation of galaxite precipitation in liquid manganese aluminosilicate matrix.

4.1.6 CaO-Al2O3 (Calcium aluminate)

Calcium metal has commonly been utilized in inclusion shape control. In aluminumkilled steel, calcium addition can readily convert the solid alumina inclusions to liquid calcium aluminates. The driving force for this phenomenon can be illustrated in the CaO-Al2O3 phase diagram shown in Figure 2-7. Small amount of CaO dissolution can significantly lower the melting point of Al2O3, which favours the merger of the two oxides. In the present work, calcium-containing inclusions were observed to be binary oxides and ternary oxides; no separate oxide in the form of calcia (CaO) was found. An example of typical single-phase calcium aluminate inclusion is given in Figure 4-19. Calcium aluminate inclusion in spherical shape usually indicates molten state in the steel bath and retains its shape upon solidification.

Figure 4-19: Oxide inclusions found in 1018S ladle tap sample: calcium aluminate

52

The behaviour of calcium in molten steel at 1600C is still uncertain and it remains unclear whether calcium operates as a direct deoxidizer, which can be described by gasliquid interaction models, or it simply decreases the activity of silica by forming a complex oxide, thereby improving the overall deoxidizing effect. Most of the CaO-containing inclusions were deemed to be exogenous in origin due to 1) calciums insolubility in steel thus making direct indigenous deoxidation unlikely to occur, 2) frequent reactions between steel and slag as well as steel and refractory materials, and 3) physical erosion of refractory materials and entrainment of slag. In addition to Ca-Si charges, refractory materials and metallurgical slags serve as exogenous sources of CaO. Refractory materials, such as dolomite, used in steelmaking vessels often contain both CaO and Al2O3. Lime, CaO, is a component of most slag used in steel refining and melt covers. It is, however, possible that a CaO-containing inclusion can form by starting with exogenous nuclei follow by indigenous growth. On the contrary, inclusions resulting from coalescence of indigenous inclusions with exogenous CaO sources such as calcium aluminate slag are also highly probable. Though rare, calcium aluminates free of MgO and containing trace amounts of MnO or SiO2 are likely products of the deoxidation process and indigenous in nature (Figure 4-19 and 4-20).[5] In order to establish the formation mechanism of specific calcia-rich inclusions, detailed identification of phases and elements present is often necessary. Determination of calcium aluminates origin has been particularly challenging in the present investigation, given inclusion morphology and EDS spectra being the sole data. Throughout the calcium aluminate inclusions found in the samples, the effective calcium content has little influence on particle morphology. Morphology of calcium aluminate inclusion is mostly globular. Four modifications, according to stoichiometric composition, of calcium aluminate inclusions were observed: 12CaO7Al2O3 (Figure 4-20 and 4-26) CaOAl2O3 (Figure 4-21) CaO2Al2O3 (Figure 4-22, 4-24, and 4-25) 53

CaO6Al2O3 (Figure 4-23)

CA

CA
G

Figure 4-20: Oxide inclusions found in 1018S furnace tap sample: calcium aluminate (CA) and galaxite (G) The two examples of 12CaO7Al2O3 inclusions differ by the presence of SiO2 in the inclusion shown in Figure 4-26 whereas the inclusion shown in Figure 4-20 is free of SiO2. Here a distinction can be made between SiO2-containing CaO-Al2O3 inclusions and those free of SiO2. It would seem that the morphology of those CaO-Al2O3 inclusions with SiO2 tends to deviate from spherical appearance towards irregular shape (Figure 424 and 4-25) and dendrites (Figure 4-26). CaO-Al2O3 with high SiO2 content, shown in Figure 4-27, is often observed as a single-phase glassy particle of diameter greater than 30 m. Inclusions without SiO2 and having an Al2O3 content greater than 60 wt% are characterized by higher hardness[5]. They usually remain spherical upon rolling or follow brittle response by breaking up into smaller particles if severe deformation of the surrounding steel occurs[1].

54

It is conceivable that the porous structure in the calcium aluminate inclusion, shown in Figure 4-21, is a result of gas evolution followed by rapid cooling. The calcium aluminate inclusion in Figure 4-25, on the other hand, underwent solidification shrinkage as indicated by the cracks within the void.

voids CA

Figure 4-21: Oxide inclusions found in A529 ladle sample: calcium aluminate (CA) CaO2Al2O3 phase was found to crystallize as thin lathes in an aluminate matrix having similar composition corresponding to CaO2Al2O3. (Figure 4-22, 4-24, and 4-25) This observation is in good agreement with literature[1]. Presence of MgO in calcium aluminate inclusions (Figure 4.22, 4-23 and 4-24) often indicates exogenous sources since calcium containing deoxidizers are generally magnesium free. Calcium inclusions with high MgO content most likely originate from magnesia refractories by erosion or by reaction between slag and refractories. However, the raw material charged into the EAF for making the current steel samples is mainly scrap steel containing trace MgO, therefore this may contribute to the trace MgO detected in the inclusions. The strong influence of refractory composition on calcium aluminate inclusions emphasizes the

55

importance of a thorough knowledge on details of specific steelmaking practice while assessing inclusions origin.

Figure 4-22: Oxide inclusions found in A529 furnace tap sample: calcium aluminate

Figure 4-23: Oxide inclusions found in 1018S ladle tap sample: calcium aluminate 56

Figure 4-24: Oxide inclusions found in A529 tundish sample: calcium aluminate

Figure 4-25: Oxide inclusions found in 1018S ladle sample: calcium aluminate 57

Figure 4-26: Oxide inclusions found in 1018S ladle sample: calcium aluminate

Figure 4-27: Oxide inclusions found in 1018S ladle sample: calcium aluminate with high silica content 58

4.1.7 CaO-SiO2 (Calcium silicate)

In the study involving calcium-containing inclusions, the practical objective is to distinguish calcium-aluminates from calcium-silicates as their difference in response to deformation can significantly affect the cleanliness of steel. Such differentiation is also important in establishing the inclusions origin since most of the calcium silicates belong to common Ca-Si deoxidation products while majority of calcium aluminates tend to follow the scheme of indigenous growth on exogenous nuclei.[5] Partial substitution of CaO by MnO and FeO was common to all calcium silicate inclusions found. (Figure 4-28) This type of inclusion shows little to no solubility of MgO. Calcium aluminates, on the other hand, have been found to replace CaO with MgO up to several percent. However, the characteristic substitution of CaO with MnO in calcium silicates is absent in calcium aluminates. Therefore, detection of noticeable MgO content or considerable amount of MnO can be used to differentiate calcium silicate and calcium aluminate inclusions.

Figure 4-28: Oxide inclusions found in 1018S billet sample: calcium silicate

59

Differentiation among aluminates and silicates can also be made by the study of rolled metal samples. Unlike calcium aluminates, calcium silicate inclusions exhibit similar deformation behaviour as the manganese silicate inclusion shown in Figure 4-15. As for calcium aluminate inclusions, the deformation pattern has been described by Kiessling[1] as strings of crystals. It was also mentioned in his report that work-induced crystallization of calcium aluminates is highly probable, whereas calcium silicates typically remain glassy. Calcium silicate inclusions observed in the current work mostly consist of homogenous monophase, often glassy in appearance, spherical droplets. During the investigation, some heterogeneous calcium silicates were found to be holding together corundum, galaxite and other spinel type inclusions as shown in Figure 4-29. Such agglomerates (Figures 4-6, 4-20 and 4-29) are more harmful to the materials mechanical properties than in the form of their individual constituents.

C CS

Figure 4-29: Oxide inclusions found in 1018S furnace tap sample: calcium silicate (CS) and corundum (C)

60

In general, CaO-content in inclusions was found to be higher in the ladle samples and saw a decrease during tapping. However, calcium-containing inclusions identified in the tundish samples were often high in CaO, possibly due to ladle calcia-rich slag entrapment. An example of such silicate inclusion is shown in Figure 4-30.

Figure 4-30: Oxide inclusions found in A529 tundish sample: calcium silicate

4.1.8 CaO-Al2O3-SiO2 (Calcium aluminosilicate)

The ternary calcium aluminosilicate inclusions are also common products of Ca-Si deoxidation. CaO-Al2O3-SiO2 phase differs from binary calcia phases (CaO-Al2O3 and CaO-SiO2) in that solubilities of MnO, FeO, and MgO have been observed in the lowmelting point ternary oxide phase. They exist as metastable monophase inclusions in solid steel since the cooling rate associated with common steelmaking practices is often too fast for secondary phase precipitation to occur. Clues to establishing the origin of calcium aluminosilicate inclusions lie with the amount of CaO and MgO present as well as the CaO:MgO ratio. Inclusions origin assessment is often based largely on the steelmaking practice associated with the specimen, especially for ternary inclusion phase

61

like calcium aluminosilicate since there is no crystalline phase that can be utilized as an indicator. Inclusion particle shown in Figure 4-31 is low in CaO and high in silica, alumina and manganosite. This composition is typical for deoxidation products that likely have indigenous origin; which is reinforced by the absence of MgO, implying the lack of refractory participation while low CaO-content effectively indicated inclusions minimum interaction with the slag.

Figure 4-31: Oxide inclusions found in A529 ladle tap sample: calcium aluminosilicate On the contrary, the composition of calcium aluminosilicate inclusion shown in Figure 432 suggests exogenous origin from refining slag. High CaO-content inclusion with relatively less silica, alumina and manganosite is usually associated with turbulent slag mixing during argon stirring. This inclusion being a Ca-Si deoxidation product, an alternative origin, is less probable, mainly due to the SiO2:CaO ratio being less than unity. No solid sulphide solubility has been reported for calcium aluminosilicate

62

inclusions. The sulphide signal is believed to have resulted from the MnS scale (see Section 4.1.9.) on the inclusions surface.

Figure 4-32: Oxide inclusions found in 1018S ladle sample: calcium aluminosilicate

4.1.9 MnS (Manganese sulphide)

Sulphur is soluble in iron at steelmaking temperature, therefore no formation of common metal sulphides are expected throughout the molten steel operations. As the liquid steel solidifies, solubility of sulphur decreases to about 0.05 wt% S at 1365C and further cooling to 988C decreases the solubility limit to 0.012 wt% S.[4] During steel solidification, insoluble sulphur segregates and forms metal sulphides with iron and manganese. Stability of the two sulphides are comparable at steelmaking temperature, but MnS is the more stable phase at room temperature.[1] Although smaller in particle diameter, sulphide inclusions were found in greater quantity than oxide inclusions. Sulphide precipitates were frequently observed in all specimens as a result of decrease in solubility upon cooling, which may not truly reflect the condition 63

at liquid steel temperature. Therefore only sulphides found in billet samples are discussed in this section. Unlike oxide inclusions in previous sections, MnS inclusion is often more difficult to locate due to smaller particle size and lack of contrast in polished sections, as illustrated in Figure 4-33. Three-dimensional morphology of MnS inclusions, taken from the same area, is depicted in Figure 4-34. This type of MnS inclusion, showing globular form, is often referred to as type I sulphide.

Figure 4-33: Sulphide inclusions found in 1018S billet sample: manganese sulphide At room temperature range, type I sulphides are generally regarded as highly deformable inclusions; behave much like glassy silicates at elevated temperatures. (See Sections 4.1.4 and 4.1.7) Therefore type I sulphides generally have minimum impact on steels fatigue properties. In contrast, type II sulphides follow dendritic crystallization at the grain boundaries in steel commonly produced by ingot casting. Type III sulphides are monophase particles characterized by random distribution in steel and faceted morphology. No type II or type III sulphides were observed in the present work.

64

Figure 4-34: Sulphide inclusions found in 1018S billet sample: manganese sulphide It has been reported by Kiessling and Westman[7] that MnS phase has extended solubility of vanadium, chromium, iron and cobalt as well as small amount of titanium and nickel. In this study, a number of MnS inclusions, shown in Figures 4-34 and 4-35, have been identified to show small amount of copper solubility. No FeS phase has been identified in this investigation due to high manganese content in the steel samples. The condition for FeS formation requires the steel to be free of manganese and rich in sulphur. MnS inclusions observed in the specimen were repeatedly found to contain iron in solid solution. The amount of iron present in solution with MnS can impact the deformation response, which in turn affects the machinability of the steel.[7] The amount of iron present in MnS is mostly dependent on the sulphur content in steel, sulphur solubility in liquid steel and the cooling rate associated with casting operation. The control of sulphur content in steel as well as the Mn:S ratio can influence the resultant sulphide composition. Evidently, the iron content in MnS inclusion increases with increasing sulphur content in steel.[8] The solubility of sulphur, however, is 65

dependent on oxygen content in the steel; where sulphur solubility is lowered under the presence of higher residual oxygen. It is possible to have iron content greater than equilibrium value if the inclusion is cooled rapidly from liquid steel temperature.

Figure 4-35: Sulphide inclusions found in A529 billet sample: manganese sulphide Good sulphide inclusion retention on samples surface was achieved by SPEED etching technique. The variations of sulphide morphology, spherical and cubic, are shown in Figures 4-34, 4-35, 4-36, and 4-37; where the images were taken from SPEED etched samples. It is otherwise difficult to present the details of surface feature on inclusions, shown in Figures 4-36 and 4-37. Referring to the work by Liu et al[8], the dark fine precipitates observed on the surface of MnS inclusions were believed to be copper sulphides hence the trace copper signal shown in the EDS spectra.

66

Figure 4-36: Sulphide inclusions found in A529 billet sample: manganese sulphide

Figure 4-37: Sulphide inclusions found in A529 billet sample: manganese sulphide additional morphologies 67

Duplex inclusions, shown in Figure 4-38, are common type I sulphide variations; characterized by sulphide scales/shell on oxides. Inclusions shown in Figure 4-39 are three-dimensional representation of duplex inclusions, illustrating sulphide patches on oxides. Two different formation mechanisms are generally accepted.[1] Upon steel solidification, existing oxides (M in Figures 4-38 and 4-39) such as aluminates and silicates, are low-energy nucleation sites for sulphide precipitation (S in Figures 4-38 and 4-39). Alternatively, the sulphide scale may precipitate from sulphur-rich molten silicate during cooling. Studies[4] have shown that when brittle oxides are coated by sulphides, the negative effect of oxide inclusions on fatigue properties is minimized. The overall inclusions thermal expansion coefficient can achieve a comparable value to that of steels thus minimizing interfacial stress.

S M M

S M

S
M S

Figure 4-38: Sulphide inclusions found in 1018S billet sample: manganese sulphide scale (S) around silicate matrix (M) 68

S M M

M S

Figure 4-39: Sulphide inclusions found in 1018S billet sample: manganese sulphide scale (S) around silicate matrix (M)

4.1.10 Development of inclusion species during steelmaking

The steel cleanliness depends much on the melting and casting practices where a varied operation often results in notable differences in total oxygen, total amount of inclusions indicated by total number of inclusions or area fraction of inclusions, particle size distribution as well as the types of inclusion present. A comparison of the inclusion types present in steel grades A529 and 1018S is given in this section. Both EAF steels were produced with identical deoxidation practice and were similar in overall composition as shown in Table 3-1; however, the steelmaking operations associated with the two steel grades differ in melt protection during vessel transfer. Refractory nozzle was implemented for the production of A529 steel samples whereas the 1018S steel samples were produced with both refractory nozzle and inert gas shrouding. The inclusion types present in A529 and 1018S steel are summarized in Table 4-1 and Table 4-2 respectively.

69

Table 4-1: Summary of inclusion types present in A529 steel

S tee lm ak in g S tep In c lus io n S p ec ies F u rn a ce tap L a d le L a d le ta p T u n d ish Billet

A l2O 3 S iO 2 (F e, M n )O M nO -S iO 2 M nO - A l 2 O 3 C aO - A l 2 O 3 C aO -S iO 2 C aO - A l 2 O 3 -S iO 2 M nS , (F e, M n)S

Table 4-2: Summary of inclusion types present in 1018S steel

S tee lmak in g S tep Inc lu s io n S p ec ies F u rn a ce ta p L a d le L a d le t a p T u n d ish Bil let

A l2 O 3 S iO 2 (F e, M n )O M nO -S iO 2 M nO -A l 2 O 3 C aO -A l 2 O 3 C aO -S iO 2 C aO -A l 2 O 3 -S iO 2 M nS , (F e, M n)S

70

It is important to keep in mind the effects of cooling rate on inclusion species. The varied degree of supercooling can retain some non-equilibrium inclusion phases while suppressing the nucleation of other phases. Lollypop samples taken at furnace tap, ladle, ladle tap and tundish experienced higher cooling rate due to smaller volume. Quenching of these steel samples contribute to preserving the inclusion types present at steelmaking temperature. Primary steelmaking The inclusions species present in the furnace tap samples are similar between the steel operations. The presence of CaO-SiO2 in 1018S furnace tap samples implied furnace slag entrainment due to excess turbulence at slag-metal interface. The glassy silicate inclusions found in this process stage is often characterized with low calcium as shown in Figure 4-29. Secondary steelmaking Addition of deoxidizers including ferromanganese, ferrosilicon, silicomanganese, calcium-silicon, and small amount of aluminum bars were made at the tap ladle. The changes in composition of inclusion species present in the ladle samples can be derived from alloy addition and deoxidization products. One of the main objectives of the refining period in ladle operation is the removal of detrimental inclusions, often marked by large particle size and specific inclusion types. The detrimental inclusions types named by various steelmakers[9], in the order of increasing harmfulness, are CaO-SiO2 system, CaO-Al2O3 system and Al2O3. However, complete removal of these harmful inclusions by flotation is not feasible given limited ladle holding time. Therefore, it is evident that ladle operation also aims at the conversion of binary oxides to low melting point glassy oxides such as CaO-Al2O3-SiO2 and MnO-Al2O3-SiO2. Ternary oxides were first found in the ladle samples of 1018S steel and in the ladle tap samples of A529 steel as shown in Tables 4-1 and 4-2.

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Continuous casting In order to minimize ladle slag carry over into tundish, the bottom-pouring ladles were equipped with electromagnetic-type slag detection system. Straight refractory nozzle was used for protecting molten steel stream against reoxidation. For 1018S steel samples nitrogen gas mixture was used in conjunction to provide an improved shrouding system thus prevent reoxidation. Submerged entry nozzle (SEN) and sliding nozzle combination were used to facilitate steel flow rate and to protect liquid steel from potential reoxidation during tundish to mold transfer. As liquid steel approaches to the continuous caster, calcium aluminates and most of the calcium silicates were converted to ternary glassy (Ca, Mn)O-Al2O3-SiO2 at tundish (1018s steel)) and at billet (A529 steel). It is clear that throughout the melting and casting operations, inclusion species tend to develop from simple primary oxides to complex binary and ternary oxides. Trace sulphide inclusions were consistently found in both tundish samples from A529 and 1018S steel grades. Sulphide nucleation is facilitated by low oxygen potential in the liquid steel, which matches the tundish condition.

4.2 Quantitative Assessment

Two specimens were studied for each steelmaking operation from each of the two steel grades, for a total of 20 samples. For each sample, 40 data images were systematically taken, where images are 1.5mm apart from one another, using backscattered electron imaging mode. Therefore, the cleanliness result of each steelmaking operation is based on the analysis of 80 data images. Three cleanliness measures are discussed in this section: Particle size distribution Maximum particle size Inclusion area fraction

Particle size distribution provides an overview of steel sample cleanliness. Maximum particle size is no doubt an important requirement considering product performance is 72

mostly affected by macro-cleanliness of the steel. Inclusion area fraction is also a common cleanliness measure that offers complementary information to size distribution.

4.2.1 Particle size distribution

Results of inclusion particle size distribution of the two steel grades are summarized in Figures 4-40 and 4-41. Detailed particle size distributions for each of the five sampling locations are given in Appendix B (1018S steel) and Appendix C (A529 steel). Compared to samples taken at furnace tap, the inclusion count in ladle tap was reduced by 79% and 45% for 1018S and A529 steels respectively. The reduction of inclusion count in the ladle and ladle tap samples reflects well-controlled argon bubbling hence the effective inclusion removal by flotation. Depending on sampling location, deoxidation inclusions with particle size less than 10 m account for 66-92% and 77-92% of total inclusion count in 1018S steel and in A529 steel respectively. 9% of total inclusions found in the 1018 ladle samples have particle size greater than 30 m, which is deemed detrimental to product properties by many steelmakers[9]. However, the same 9% of the total inclusion count, or 79 inclusions/cm2, embodies 93% of the total inclusion area. Moreover, the single largest inclusion found in the 1018S ladle samples is responsible for 35% of the total inclusion area, whereas 66% of total inclusion count, having particle size less than 10 m, would only represent about 4.5% of the total inclusion area. It is therefore clear that the control and removal of macro-inclusions is vital to steel cleanliness. According to the size distribution plots, reoxidation is common to both steel grades. Reoxidation of tundish melt can arise from air entrainment, tundish slag reoxidation, and tundish refractory reoxidation. During tundish filling, negative pressure develops in the refractory nozzle connecting ladle and tundish. Air entrainment may take place if proper sealing or inert gas flushing was not applied. Traditional tundish slag former often consists of silica powder and limestone. Tundish melt is prone to reoxidation if the silica 73

3000

2500

Number of inclusions (/cm^2)

2000

1500

1000

500

0 Furnace Tap Ladle Ladle Tap <10 um 10-30 um >30 um Tundish Billet

Figure 4-40: Inclusion size distribution of 1018S

4000

3500

Number of inclusions (/cm^2)

3000

2500

2000

1500

1000

500

0 Furnace Tap Ladle <10 um Ladle Tap 10-30 um >30 um Tundish Billet

Figure 4-41: Inclusion size distribution of A529 74

content is too high in the slag. Reoxidation of tundish melt can also take place at the metal-refractory interface. If olivine content (FeO-containing component) is high in the refractory material, reduction of FeO at the tundish lining can oxidize the tundish melt. For 1018S steel, inert gas flushing was employed during melt transfer between ladle and tundish. The major contribution to the reoxidation of 1018S tundish melt is therefore likely from refractory reoxidation as well as possible slag entrainment during tundish filling. In addition to potential slag and refractory reactions, it is speculated that reoxidation in the A529 tundish melt is mostly a result of primary oxide nucleation due to ingress air, since inert gas shrouding was not applied. The above hypothesis is in good agreement with the size distribution shown in Appendices B and C. The total inclusion counts for billet samples are 1352/cm2 (1018S) and 3846/cm2 (A529); showing 65% reduction in samples with inert gas protection. (Figure4-42) The enormous increase in intermediate-sized inclusion count (10-30 m) found in the A529 billet samples is likely a result of melt reoxidation by uncontrolled atmosphere in the tundish.

5000 4500

Number of inclusions (/cm^2)

4000 3500 3000 2500 2000 1500 1000 500 0

FurnaceTap

Ladle

LadleTap 1018S A 529

Tundish

B illet

Figure 4-42: Comparison of total inclusion count 75

4.2.2 Maximum particle size

The maximum particle size plot is essential to macro-cleanliness study in indicating the specific process stage where the most harmful inclusion is generated. Figures 4-43 and 444 are plots showing change in maximum particle size throughout the melting and casting operations of the two steels. As indicated by both Figures 4-40 and 4-43, the critically sized inclusions of the 1018S steel samples were found in the ladle and were subsequently removed. For A529 steel samples, the critically sized inclusions were first found in the tundish and were subsequently carried into billet samples. Figure 4-45 is a comparison between the two melt-protection practices, which reflects the benefit of inert gas shrouding during ladle-tundish melt transfer. The maximum inclusion particle found in the A529 billet sample is approximately three times the size of that found in the 1018S billet samples.

700 600

Maximum particle size (um)

500 400

300 200 100 0

Furnace Tap

Ladle

Ladle Tap

Tundish

Billet

Max Particle Size (m ) Furnace Tap Ladle Ladle Tap Tundish Billet 95 26 492 140 35 11 73 22 69 20

Figure 4-43: Maximum particle size plot of 1018S steel samples

76

280 240

Maximum particle size (um)

200 160

120 80 40 0

Furnace Tap

Ladle

Ladle Tap

Tundish

Billet

Max Particle Size (m ) Furnace Tap Ladle Ladle Tap Tundish Billet 57 11 54 9 51 5 196 39 204 44

Figure 4-44: Maximum particle size plot of A529 steel samples

700

600

Maximum particle size (um)

500

400

300

200

100

Furnace Tap

Ladle

Ladle Tap 1018S A529

Tundish

Billet

Figure 4-45: Comparison of maximum particle size 77

4.2.3 Inclusion area fraction

Inclusion area fraction provides complementary information to total oxygen analysis and inclusion particle size distribution. After ladle refining, inclusion area fraction is reduced from 2494 ppm to 90 ppm for the 1018S steel samples and 284 ppm to 213 ppm for the A529 steel samples. (Figures 4-4647) This result is in good agreement with inclusion particle size distribution shown in Figures 4-40 and 4-41. Figure 4-48 is a comparison between the two melt-protection practices, which illustrates the effects of casting speed on steel cleanliness. The inclusion area fraction found in the A529 billet sample is approximately twice that found in the 1018S billet samples.

3500 3000 2500 2000

Inclusion area fraction (ppm)

1500 1000 500 0

Furnace Tap

Ladle

Ladle Tap

Tundish

Billet

Area Fraction (ppm ) Furnace Tap Ladle Ladle Tap Tundish Billet 548 119 2494 554 90 17 528 128 512 113

Figure 4-46: Inclusion area fraction of 1018S steel samples

78

1400 1200 1000 800

Inclusion area fraction (ppm)

600 400 200 0

Furnace Tap

Ladle

Ladle Tap

Tundish

Billet

Area Fraction (ppm ) Furnace Tap Ladle Ladle Tap Tundish Billet 327 36 284 28 213 17 602 61 1047 108

Figure 4-47: Inclusion area fraction of A529 steel samples

3500

3000

Inclusion area fraction (ppm)

2500

2000

1500

1000

500

Furnace Tap

Ladle

Ladle Tap 1018S A529

Tundish

Billet

Figure 4-48: Comparison of inclusion area fraction 79

4.2.3 Backscattered electron image analysis (BSE-IA) in steel cleanliness study

Several quantitative methods for inclusion detection and counting have been summarized by Zhang et al[10]: Optical Microscopy with Image Analysis (OM-IA), Slime Extraction, Optical Emission Spectrometry with Pulse Discrimination Analysis (OES-PDA), Liquid Metal Cleanliness Analyzer (LIMCA), Magnetic Particle Method, Mannesmann Inclusion Detection by Analysis Surfboards (MIDAS),

SEM is a common tool repeatedly found in studies involving inclusion particle morphology and deformation response but rarely does SEM find application for inclusion quantification. However, the present work has proposed and confirmed its applicability, as an inclusion quantification system utilizing image analysis tool (IA) to process the data images, taken by backscattered electron microscopy (BSE). The image acquisition with SEM is both labour-intensive and time-consuming and is often the rate-determining aspect. To improve the method efficiency, conventional SEM can be installed with a computer-control motorized sample stage in the SEM sample chamber. With the same given time, larger pool of data samples can be evaluated thus obtaining statistically significant results. Although both BSE-IA and OM-IA have good repeatability and were both capable of employing standard cleanliness analysis procedures such as ASTM-E45, an automated BSE-IA system has the following advantage over the conventional OM-IA technique: BSE-IA facilitates the removal of faulty signals from voids, scratches and other surface defects, so that they are not counted as inclusions; achieving accurate representation of samples cleanliness. During automatic survey scan, simultaneous recording of semi-quantitative composition of inclusion particles using built-in EDS can rapidly map the distribution of various inclusion species as well as the changes in composition.

80

The quality of sample polishing required by BSE-IA method is less stringent than that of OM-IA. BSE-IA method provides superior resolution and contrast compare to OM-IA.

4.3 References

[1] R. Kiessling and N. Lange, Non-metallic inclusions in steel, The Institute of Materials (London), 1978, pp. 45-79 [2] C. Benedicks and H. Lofquist, Non-metallic inclusions in iron and steel, Chapman and Hall, London, 1930 [3] T.R. Allmand, Microscopic identification of inclusions in steel, BISRA, London, 1962 [4] E.T. Turkdogan, Fundamentals of Steelmaking, The Institute of Materials (London), 1996, pp. 181-182 [5] T. Ototani, Calcium Clean Steel, Springer-Verlag, New York, 1986, pp. 64-69 [6] H. Jacobi and K.Wunnenberg, Methods for determination of oxide cleanness in steel, IISI Study on Clean Steel, International Iron and Steel Institute, Belgium, 2004, pp. 307-309 [7] R. Kiessling and C. Westman, Sulfide Inclusions and Synthetic Sulfides of the (Mn,Me)S-type, JISI, 1966, no. 204, pp. 377-379 [8] Z. Liu, Y. Kobayashi, F. Yin, M. Kuwabara, and K. Nagai, Nucleation of Acicular Ferrite on Sulfide Inclusion during Rapid Solidification of Low Carbon Steel, ISIJ International, 2007, vol. 47, no. 12, pp. 1781-1788 [9] M. Sumida, M. Nadif, M. Burty and V. Tusset, Industrial practice worldwide ULC and LC steel grades, IISI Study on Clean Steel, International Iron and Steel Institute, Belgium, 2004, pp. 365-406 [10] L. Zhang, B.G. Thomas, X. Wang, and K. Cai, Evaluation and Control of Steel Cleanliness Review, 85th Steelmaking Conference Proceedings, ISS-AIME, Warrendale, PA, 2002, pp. 431-452

81

CHAPTER FIVE: CONCLUSIONS

5.1 Conclusions

1. A novel procedure SPEED-SEM-IA for steel cleanliness assessment was carried out on 1018S and A529 steels. The qualitative aspect consists of morphology and inclusion phase characterization, which was achieved with SPEED etching and SEM observation. The quantitative aspect evaluates inclusion size distribution, macrocleanliness and amount of inclusions. The analysis method involved the combination of image acquisition (SEM-BSE) and image analysis (IA). 2. Four different image acquisition techniques were evaluated for the quantitative analysis of inclusions and it was found that SEM-backscattered electron imaging mode is the most suitable choice. 3. For inclusion morphological observation, good three-dimensional images of sulphides, alumina, and galaxite phases were obtained using the SPEED-SEM technique. The following inclusion types were frequently observed in this study using SEM and compositions were analyzed using EDS: Al2O3, SiO2, (Fe, Mn)O, MnOSiO2, MnO-Al2O3, CaO-Al2O3, CaO-SiO2, CaO-Al2O3-SiO2, MnS and (Fe, Mn)S. 4. Throughout the melting and casting operations, inclusion species tend to develop from simple primary oxides to complex binary and ternary oxides. With reoxidation minimized by gas shrouding between ladle and tundish, three steel cleanliness improvements were achieved: I) reduction in total inclusion count by 65%, II) reduction of maximum particle size by up to 66%, III) reduction in inclusion area fraction by over 50%.

82

5.2 Future Work

1. Analytical technique such as electron microprobe analyzer should be used in addition to SEM/EDS for precise composition determination of inclusion phases. Monitor the change of key elements such as calcium, aluminum, silicon, manganese, magnesium and iron in inclusions throughout the melting and casting operations. 2. Evaluate available etching techniques and develop phase-specific electrolyte in the interest of preserving various calcium-containing silicate and aluminate phases for deep etching observation. 3. Correlate the development of inclusion composition and count in the furnace, ladle, tundish and mold slags with inclusions found at each respective steelmaking vessel. 4. Utilize containerless levitation melting technique to investigate the thermodynamic aspect of inclusion formation. Explore the feasibility of inclusion isolation onto droplets surface for quantification purpose.

Figure 5-1: Proposed levitation apparatus 83

APPENDICES
Appendix A: Inclusions Effect on Fatigue Behaviour

Both A529 and 1018S high strength alloy steel end products are often utilized in structural applications. Fatigue failure, frequently caused by non-metallic inclusions, should be taken as the primary consideration when evaluating steel cleanliness for load bearing applications. The types of inclusions having detrimental effects on fatigue properties are, in the order of increasing severity, sulphides, silicates, non-deformable spherical inclusion (simple oxides, nitrides, and aluminates), alumina. In terms of fatigue properties, the presence of silicate inclusions is more harmful than sulphide inclusions. At the service temperature, silicates usually have limited ductility.[1] As matrix steel deforms under cyclic load, silicates do not deform, thereby producing microcracks at the steel-inclusion interface. Studies[2-3] also show that thermal expansion coefficient () of inclusions and the type of steel plays a role in determining which inclusion types are more harmful than others. Alumina, nitrides, spinel, silicates and calcium aluminates have lower values than that of common structural steels. The difference in value can lead to internal stress (negative deviation) or microvoid formation (positive deviation).

Reference: [1] S. Millman and K.Y. Lee, Industrial practice Linepipe grades, IISI Study on Clean Steel, International Iron and Steel Institute, Belgium, 2004, pp. 409-442 [2] D. Brooksbank and K.W. Andrews, Stress fields around inclusions and their relation to mechanical properties, Journal of the Iron and Steel Institute, UK, 1972, Vol. 210, pp.246-255 [3] E.T. Turkdogan, Fundamentals of Steelmaking, The Institute of Materials (London), 1996, pp. 291-293 84

Table A: Coefficient of thermal expansion of various inclusion types[2] Inclusion type Coefficient of thermal expansion, , 0-800C, (10-16 K-1) Al2O3 and MnOAl2O3 MnOSiO2 12CaO7Al2O3 CaOAl2O3 CaO2Al2O3 CaO6Al2O3 CaOSiO2 MnS 7.95 9.55 7.73 6.59 5.00 8.86 10.91 18.07 Deviation from 1% C-Cr bearing steel (10-16 K-1) - 4.55 - 2.95 - 4.77 -5.91 - 7.5 - 3.64 - 1.59 5.57

Appendix B: Inclusion Particle Size Distribution of 1018S Samples

Inclusion Size Distribution: 1018S - Furnace Tap

10000

1000

Number of inclusions (/cm^2)

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

85

Inclusion Size Distribution: 1018S - Ladle

10000

1000

Number of inclusions (/cm^2)

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

Inclusion Size Distribution: 1018S - Ladle Tap

10000

1000

Number of inclusions (/cm^2)

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

86

Inclusion Size Distribution: 1018S - Tundish

10000

Number of inclusions (/cm^2)

1000

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

Inclusion Size Distribution: 1018S - Billet

10000

1000

Number of inclusions (/cm^2)

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

87

Appendix C: Inclusion Particle Size Distribution of A529 Samples

Inclusion Size Distribution: A529 - Furnace Tap

10000

1000

Number of inclusions (/cm^2)

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

Inclusion Size Distribution: A529 - Ladle

100000

10000

Number of inclusions (/cm^2)

1000

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

88

Inclusion Size Distribution: A529 - Ladle Tap

10000

1000

Number of inclusions (/cm^2)

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

Inclusion Size Distribution: A529 - Tundish

10000

1000

Number of inclusions (/cm^2)

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

89

Inclusion Size Distribution: A529 - Billet

10000

Number of inclusions (/cm^2)

1000

100

10

1 <5 5--10 10--15 15--20 20--25 25--30 30--35 35--40 40--45 45--50 >50 >100 >200

Inclusion particle size (um)

90