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Master of Technology
In
Metallurgy Engineering
(Specialization in Steel Technology)
By
DEEPAK PATEL
(QUROOPHQW1R$'
I the undersigned solemnly declare that the report of the thesis work entitled Study of the nonmetallic inclusions and their effect on the properties of steel is based on my own work carried
out during the course of my study under the supervision of Dr. Varsha Chauraisa, Sr. Associate
Professor and H.O.D., Department of Metallurgy Engineering, U.P.U. Govt. Polytechnic,
Durg, (C.G.).
I assert that the statement made and conclusions drawn are an outcome of the project work. I
further declare that to the best of my knowledge and belief that the report does not contain any
part
of
any
work
which
has
been
submitted
for
the
award
of
any
other
_____________________
(CANDIDATE)
Deepak Patel
Roll No. 5005612005
Enroll. No. AD2437
___________________
(SUPERVISOR)
Dr.V. Chaurasia
Sr. Associate Professor
H.O.D.
Department of Metallurgy
Engineering,
U.P.U. Govt. Poly. Durg C.G.
II
ii)
iii)
Fulfills the requirement of the Ordinance relating to the M. Tech Degree of the
University and
iv)
Is up-to the standard in respect of both contents and language for being referred to the
examiners.
___________________
(SUPERVISOR)
Dr.V. Chaurasia
Sr. Associate Professor
H.O.D.
Department of Metallurgy
Engineering,
U.P.U. Govt. Poly. Durg C.G.
_____________________________________________
REGISTRAR
CHHATTISGARH SWAMI VIVEKANAND TECHNICAL UNIVERSITY
NORTH AVENUE SEC 8, BHILAI, CHHATTISGARH
III
The Thesis entitled Study of the non-metallic inclusions and their effect on the properties of
steel submitted by Deepak Patel, Roll No.: 5005612005 & Enrollment No.: AD2437 has been
examined by the undersigned as a part of the examination and is hereby recommended for the
award of the degree of Master of Technology in the faculty of Metallurgy Engineering with
specialization in Steel Technology of Chhattisgarh Swami Vivekanand Technical University,
Bhilai (C. G.).
____________________
____________________
Internal Examiner
External Examiner
Date:
Date:
IV
ACKNOWLEDGEMENT
First, I would like to express my special gratitude to my main supervisor, Dr. Varsha Chaurasia,
for her advices and encouragements during these years of studies. Her excellent guidance to see
the mind of a researcher will always be in my heart.
I am truly grateful to Dr. Ashok Srivastava, H.O.D. Met. OPJU, fo r his constant support and
valuable discussions throughout this work. His boundless energy and positive attitude were very
impressive to me for completing my work.
I am thankful for the support from JINDAL STEEL & POWER LIMITED, @ RAIGARH C.G.
regarding help with the industrial visits. I also thanks to the VP & H.O.D. of Technical Services
Department & Qua lity Control Shri B. Lax minarsimham and his team including one of my
college friend Ms. Neelam Sharma, for their valuable help throughout all industrial studies. They
have given me a great insight in both research and production process of world-class quality steel.
I specially would like to thank Professor A.K. Verma, for his encouraging advice and comments.
I sincerely respect his passion for the study and research.
Thanks to all my friends and c olleagues at the Department of Meta llurgy Engineering
U.P.U.G.P.D. for their friendship and kindness.
Finally, I would like to express my respect and gratitude to my parents for their continuous trust
and love.
Deepak Patel
June 2015
ABSTRACT
Non-metallic inclusions are a major issue during the production clean steels, as they influence
the microstructure and structural properties effectively. They are often considered as harmful
to the final product quality and to the steel processing productivity; therefore many industrial
efforts are directed towards improving inclusion removal. Another way is to use non-metallic
inclusions to produce steels with enhanced properties. In both cases, the key issue is to control
the characteristics of the inclusion population in the liquid steel, such as qu antity/limit,
composition, physical appearance or morphology, shape, size and distribution.
The application of new secondary refining techniques and non-metallic inclusion reduction
techniques in steel production processes has greatly reduced the size and amount of nonmetallic
inclusions remaining in molten steels and steel products due to which inspection of inclusions
is very difficult. The influences of inclusions on the p roperties of steels are dis cussed. As
inclusions have influence on several properties of steel, such as formability, toughness, and
machinability and corrosion resistan ce. In general, the less severe the inclusions, the higher
quality of steel. This is the reason for, analysing and assessment of non-metallic inclusions is
important for quality control.
The main part of this work has been a literature survey, reviewing the main methods used for
the characterization of inclusions in clean steels, experimental reports for information on how
steel cleanness is evaluated today, and how the steel cleanness is related to the performance of
clean steels as a product.
VI
LIST OF ABBREVIATIONS
Symbols
Units
Equilibrium constant
Temperature
T[O]
Total oxygen
ppm
Wavelength
m
kCal
K-1
Element Abbreviations
Compound Abbreviations
Al
C
Ca
Cu
Cr
Fe
O
P
Pt
Mg
Mn
N
Ni
S
Si
Al2O3
CaO
CaOAl2O3
Alumina
Calcia
Calcium aluminate
CaO SiO2
Calcium silicate
CaS
FeO
FeOAl2O3
FeS
MgO
MnO
MgOAl2O3
MnOAl2O3
Calcium sulphide
Wstite
Hercynite
Troilite
Periclase
Manganosite
Spinel
MnOSiO2
Rhodonite
MnS
SiO2
Manganese sulphide
Silica
Aluminum
Carbon
Calcium
Copper
Chromium
Iron
Oxygen
Phosphorus
Platinum
Magnesium
Manganese
Nitrogen
Nickel
Sulphur
Silicon
Galaxite
Abbreviations
ASTM
BSE
Backscattered Electron
DIC
EAF
VII
JSPL
IA
Image Analysis
LCM
OES
OM
Light-Optical Microscope
ppm
SE
Secondary Electrons
SEN
SEM
wt%
weight percentage
IS
Indian Standards
NMI
VIII
LIST OF FIGURES
Figure 1.1. A schematic diagram of the process route in SMS at JSPL
Figure 2.1: Sources of inclusions in liquid steel
Figure 2.2: Free energy of formation for various sulphides. Dash-dot line indicates equal
sulphur pressure in unit of atmosphere.
Figure 2.3: Free energy of formation for various oxides. Dash-dot line indicates equal oxygen
pressure in unit of atm.
Figure 2.4: Deoxidizing power of various elements at 1600 0C
Figure 2.5: a) As-polished (2-dimensional) steel sample showing Al2O3 dendrite b) Partial
slime extracted (3-dimensional) steel sample showing the same Al2O3 dendrite
Figure 2.6: Equilibrium relations for manganese-silicon deoxidation of steel at various
temperatures
Figure 2.7: The effect of manganese content on stability of oxide phases resulting from steel
deoxidation at 1550C (m: mullite; l: liquid manganese silicate)
Figure 2.8: CaO-Al2O3 equilibrium phase diagram.
Figure 2.9: Schematic representation of MnO-SiO2-Al2O3 ternary phase diagram
Figure 2.10: Morphology of NMIs occurred in steel
Figure 2.11: Schematic representation of mold powder entrapment
Figure 2.12. Schematic drawing of Slab caster tundish furniture
Figure 3.1: Flow chart of scheme of experiments
IX
LIST OF TABLES
Table 2-1: Possible Sources of Inclusion
Table 2-2: Stoichiometric composition of reported inclusion phases
Table 2-3: Inclusion distribution characteristics in solidified slab samples collected from
original and modified design tundish operations
Table 4-1: The importance of clean steel with respect to mechanical properties of the product
Table 4-2: Chemical composition of Grade 880 rails as per IRS T-12 2009 specifications
Table 4-3 Inclusion Rating Results
XI
TABLE OF CONTENT:
CHAPTER 1
INTRODUCTION
1.1.
1.2.
Clean steel
1.3.
CHAPTER 2
2.1 )
2.2 )
LITERATURE REVIEW
6-9
10-23
24
25
27
Clean steel
31
31
32
2.2.3 Salient steps adopted during secondary refining for Steel Cleanliness 32
2.2.4 Salient steps adopted during Vacuum Degassing for steel cleanliness 33
2.2.5 Role of continuous casting
CHAPTER 3
34
35
3.1)
Overview
36
3.2)
Quantitative Assessment
37
38
40
CHAPTER 4
42
4.1)
Introduction
43
4.2)
Experimental procedure
46
4.3)
Result
48
XII
CHAPTER 5
REFRENCES
50
53
XIII
CHAPTER 1
INTRODUCTION
mechanical properties of steel, since they can initiate ductile and brittle facture.
The type and appearance of these non-metallic inclusions depends on factors such
as grade of steel, melting process, secondary metallurgy treatments and casting of steel.
Only 1 ppm each of oxygen and sulphide will still contains 109 -1012 non-metallic
CHAPTER 2
LITERATURE REVIEW
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 a l s o d e p e n d o n
m a n g a n e s e t o S u l p h u r r a t i o . Examples of common sulphideinclusions include MnS,
FeS, (Mn, Fe)S and CaS. The Sulphur affinity of various elements can be compared with
free energy of sulphide formation. Figure 2.1.2 gives a plot of curves for common elements
found in steelmaking.
Figure 2.2: 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. [R.H. Tupkary , 2012][12] 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.
9
10
STEEL DEOXIDATION
Maximum solubility of oxygen in liquid iron at the eutectic of 1527C is about 0.16% [E.T.
Turkdogan, 1996] [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 [12].
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 [17]. The oxygen
affinity of various elements can be compared with free energy of oxide formation. Figure:
2.1.2 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 2.1.4 depicts the deoxidizing
power of various elements at 1600 C
11
Figure 2.3: Free energy of formation for various oxides. Dash-dot line indicates equal
oxygen pressure in unit of atm [4].
Four cost-effective deoxidizers are carbon, manganese, silicon, and aluminum. Carbon is
often c o n s i d e r e d a n e f f e c t i v e d e o x i d a t i o n e l e m e n t , f o r m i n g
g a s e o u s d e o x i d a t i o n 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
[Kiessling and Lange et al. 1978][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)
[2-2]
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.
The manganese deoxidation reaction,
[Mn] + [O] = (MnO)
[2-3]
13
%Mn %O
12440
For
5.33
[2-4]
[2-5]
%Mn %O
[2-6]
SILICON DEOXIDATION
It can be seen from Figure 2.1.4, 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 tetrahedral molecules. Low quartz,
high-quartz, tridymite, and cristobalite are among the common modifications [Kiessling
and Lange et al. 1978]
[6]
[2-8]
30000
T
For
11.5
[2-9]
[2-10]
ALUMINUM DEOXIDATION
From Figure 2.1.4, 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, Imodification). 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 Pm, 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. [Kiessling and Lange et al. 1978]
[6]
15
Figure 2.5: 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 super- saturation.
The resulting inclusions are finely dispersed corundum clusters [Kiessling and Lange et al.
1978] [6]
II.
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.
16
[2-11]
62780
T
For
2 3
[2-12]
%
20.5
[2-13]
[2-14]
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].
17
[2-15]
%
%
1510
T
[2-16]
1.27
[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
p h a s e s o f r e s u l t i n g d e o x i d a t i o n p r o d u c t s d e p e n d h e a v i l y o n s t e e l chemistry
and reaction temperature as illustrated in Figure 2.1.7. 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.
19
Figure 2.7: 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 2.1.3, 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) [OTOTANI et al. 1986] [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
20
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 extent of deoxidation can be improved from 8-10ppm O to 1ppm O in Alkilled steel (0.05% Al)[S MILLMAN, 2004] [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
2.1.8) and therefore exists in the liquid state at steelmaking temperatures. Moreover, there
exist five modifications of calcium aluminates as indicated in Figure 2.1.8;
12CaOx7Al2O3, 3CaOxAl2O3 and CaOxAl2O3 are liquid, while CaOx2Al2O3 and
CaOx6Al2O3 are solid at steelmaking temperatures.
21
SiO2), which has yet to be reported as an inclusion phase in the literature. According to
Figure 2.1.3, 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
other hand, Al2O3 and Cr2O3 are interchangeable at elevated temperatures due to their
structural resemblance. Corresponding inclusion phases were often reported in both MnOSiO2-Al2O3 and MnO-SiO2-Cr2O3 with notable difference in the absence of ternary
phases in the MnO-SiO2-Cr2O3 system[SOLMAN AND EVANS, 1951][5]. Corresponding
phases relating to MnO-SiO2-Al2O3, FeO-SiO2-Al2O3, and MnO-SiO2-Cr2O3.
Table 2-2: Stoichiometric composition of reported inclusion phases. [Kiessling and Lange
et al. 1978][6]
Mineral
classification
Chemical
formula
SiO2
Al2O3
Corundum
Al2O3
--
--
100
Cristobalite
SiO2
--
100
--
Tridymite
SiO2
--
100
--
Quartz
SiO2
--
100
--
Manganosite
MnO
100
--
--
Galaxite
MnO.Al2O3
41
--
59
Mullite
3Al2O3. SiO2
--
28
72
Rhodonite
MnO.SiO2
54
46
--
Tephroite
2MnO.SiO2
70
30
--
23
Globular shape of inclusions is preferable since their effect on the mechanical properties
of steel is moderate. Spherical shape of globular inclusions is a result of their formation in liquid
state at low content of aluminum. Examples of globular inclusions are manganese sulfides and
oxysulfides formed during solidification in the spaces between the dendrite arms, iron aluminates
and silicates.
and oxysulfides in form of thin films (platelets) located along the steel grain boundaries. Such
inclusions are formed as a result of eutectic transformation during solidification. Platelet shaped
inclusions are most undesirable. They considerably weaken the grain boundaries and exert adverse
effect on the mechanical properties particularly in hot state (hot shortness).
in formation of dendrite shaped oxide and sulfide inclusions (separate and aggregated). These
inclusions have melting point higher than that of steel. Sharp edges and corners of the dendrite
shaped inclusions may cause local concentration of internal stress, which considerably decrease
of ductility, toughness and fatigue strength of the steel part.
addition (after deep deoxidation by aluminum) of small amounts of rare earth (Ce,La) or alkaline
earth (Ca, Mg) elements. Due to their more globular shape polyhedral inclusions exert less effect
on the steel properties than dendrite shape inclusions.
24
Fig. 2.10: Morphology of NMIs occurred in steel [Kiessling and Lange et al. 1978][6].
2.1.4 INFLUENCE OF INCLUSIONS ON THE PROPERTIES OF STEEL
The properties that are adversely affected are fracture toughness, impact properties, fatigue
strength, and hot workability. The factors responsible for these may be classified as follows:
1. Geometrical factors: size, shape (may be designated as the ratio of major axis to minor
axis), size distribution, and total volume fraction of inclusions.
2. Property factors: deformability and modulus of elasticity at various temperatures,
coefficient of thermal expansion
From a fundamental point of view, an inclusion/matrix interface has a mismatch. This causes
local stress concentration around it. Application of external forces during working or service
can augment it. If the local stress becomes high, then microcracks develop. The propagation
of microcracks leads to fracture. Investigations have established that only large inclusions are
capable of doing this kind of damage, and this led Kiessling [6] to develop the idea of critical
size. In practice, it is customary to divide inclusions by size into macroinclusions and
25
26
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 [12]. In
addition, with careful control of stirring and flowrate monitoring, the amount of exogenous
inclusions can be minimized.
reactions between dissolved species in the steel bath and are generally smaller in size [12].
Deoxidation products originate from the reaction between dissolved oxygen and added
deoxidant 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.[19] 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 constituent.
27
Exogenous inclusions are the real cause of concern during continuous casting, arise
primarily from the incidental chemical (re-oxidation) and mechanical interaction of liquid
steel with its surroundings (slag entrainment and erosion of lining refractory)
[TURKDOGAN, 1996][3]. Air is the most common source of re-oxidation, which comes into
contact with molten metal during casting when it is poured from ladle to tundish and tundish
to mold.
29
Flow control in the tundish is the key to the production of clean steel. Different types of
flow modifiers are used in the tundish after doing mathematical modeling and water
modeling of the tundish
a. Pouring box
b.Expendables and permanent dams
c. Weirs and
d.Slotted dams.
Different combinations of pouring boxes and permanent dams are used for different
tundish at JSPL. These flow modifiers are invariably employed to protect excessive weir of
tundish refractory, dampen turbulence in the shrouding areas and to provide directional flow
of metal in order to provide nearly identical residence time to all strands in multi-strand
tundish. Pouring boxes helps in upward directional flow supports inclusion floatation and
assimilation into tundish slag. A rigorous Water Modeling study and mathematical modeling
was conducted for slab caster and Combination caster tundish to improve yield and
cleanliness of steel. Fig 2.1.12 illustrated the modified design of the slab caster tundish with
use of different type of furnitures for flow modification.
30
The inclusion rating of the collected samples from tundish before and after modification
clearly shows improvement in steel cleanliness after incorporation of the pouring box in the
slab caster tundish. Table 2-2 illustrated the inclusion level before and after modification of
slab caster tundish.
Table 2-3: Inclusion distribution characteristics in solidified slab samples collected from
original and modified design tundish operations
in slag positively maintained below 1.0%. The Celox reading for dissolved oxygen for
vacuum degassed heats aimed at 4.0 ppm max.
2.2.5
Non-metallic inclusions are the most significant cause of concern in cast steels which can
lead to field failures. Mechanical behavior of steel is controlled to a large extent by the
volume fraction, size distribution, composition and morphology of inclusions and
precipitates, which act as stress raisers. The inclusion size distribution is particularly
important, because large macro-inclusions are the most harmful to mechanical properties
though the large inclusions are far outnumbered by the small ones, their total volume fraction
may be larger [19]. Ductility & impact toughness is appreciably decreased by increasing
amounts of oxide or sulphide inclusions. Inclusions also lower resistance to Hydrogen
Induced Cracks. The source of most fatigue problems in bearing steel are hard and brittle
oxides, especially large alumina particles over 30m
[18]
extensive review on sources of inclusions during continuous casting, their morphology, and
sources of gaseous ingression in steel during casting. This also describes in detail about
various measures adopted during Continuous Casting to avoid the occurrences of the above
problems.
34
CHAPTER 3
EXPERIMENTAL ASPECTS AND
METHODOLOGY
35
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 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 fig
3-1
36
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.
dimensional 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 [15].
38
39
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
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, SEM- BSE is
chosen as the most suitable image acquisition technique for the quantitative analysis
of inclusions.
Figure 3-6: Photograph processed by image analysis showing detected area as inclusions
(a) Laser confocal microscopy, (b) SEM (backscattered electron mode)
41
CHAPTER 4
RESULT AND DISSCUSSION
42
4.1 INTRODUCTION
STEEL CLEANLINESS OF RAILS:
In order to obtain the satisfactory cleanliness of steel it is necessary to control and improve a
wide range of operating practices throughout the steelmaking processes like deoxidant- and
alloy additions, secondary metallurgy treatments, shrouding systems and casting practice.
Table 4-1: The importance of clean steel with respect to mechanical properties of the product
[12]
Element
Form
S, O Sulfide and oxide inclusions
C, N
Solid solution
Settled dislocation
Fatigue strength
Solid solution
Temper brittleness
Rail steel needs to conform to stringent quality standards described in the standards owing to
its critical nature of its application. Chemical composition range of Grade 880, which is a
common rail grade as per IRS-T12, is shown in Table 4-2.
43
Table 4-2: Chemical composition of Grade 880 rails as per IRS T-12 2009 specifications
Grade
%C
%Mn
%Si
%S
%P
%Al
Grade
0.60-
0.80-
0.10-
0.03
0.03
0.015
880
0.80
1.30
0.50
max
max
max
%Nb
-
H in
ppm
1.6
max
Hydrogen in rail is restricted to a maximum of 1.6 ppm which makes degassing necessary.
As far as inclusions are concerned, it is well known that they are detrimental to rails. IRS T12 2009 specifies that the inclusion rating level of rails, when examined as per IS: 4163, shall
not be worse than 2.5 A, B, C, D thin or 2.0 A, B, C, D thick.
EFFECT OF INCLUSIONS TO THE PHYSICAL CONTINUITY OF RAILS:
Inclusions act as the barrier to the physical continuity of metal. The area in the vicinity of
inclusion develops a local residual stress field; so that the initiation & propagation of crack
gets driven. Fatigue is the result of progressive initiation & subsequent propagation of crack.
Initiation is typically accepted to involve crack development- microcracks (size ranging from
micrometer to millimetre) transforming into macro cracks (greater than millimetre, & up to as
long as sizeable fraction of a metre). The really important crack dimension, which determines
fatigue life, is penetration into the load bearing area. Initiation is dependent on slip processes,
governed by cyclic shear stresses. Propagation is generally governed by cyclic tensile stresses
& is caused by repeated plastic stretches & blunting at the crack tip. The classic explanation
is that, when a flat crack is open by tensile stresses, stretching occurs normal to the crack tip,
thereby advancing its position. In a generally compressive field, such as that under a wheel
contact, early growth by shear is the only possible mechanism available to advance the crack.
Later, under the influence of bulk bending stresses in the body of rail, the crack grows by
tensile opening & closing. The extremely high contact stresses & the enormous power density
(i.e the power passing through per unit) concentrated at the contact under the vertical loads,
are enhanced by lateral (curving) longitudinal (traction & braking) loads. In these
44
45
Fig 4-2 Sample images taken @ TSD, JSPL for inclusion rating
46
4.2.7
Group A (Sulphide Type) highly malleable, individual grey particles and generally
rounded ends.
Group B Alumina - Numerous and non-deformable, angular, black or bluish particles
(at least 3) aligned in the deformation direction.
Group C Silicate - highly malleable, individual black or dark grey particles and
generally sharp ends.
Group D Globular Oxide non deformable, angular or circular, black or bluish
randomly distributed particle.
4.2.8
The image is projected on the ground glass and a clear plastic overlay is placed over
the ground glass projection screen.
4.2.9
The image within the test square is compared with the standard chart diagrams of IS:
4163 Specification.
4.2.10 The entire polished surface is examined. Randomly any ten numbers of worst fields
are chosen and each field is compared with the standard chart for each type of
inclusion.
4.2.11 In each worst field, for each type of inclusion, total length of the inclusion is
measured and corresponding severity number is noted down from the comparison
chart of IS: 4163 specification
47
4.2 RESULT
Table 4-3 Inclusion Rating Results
Heat ID
A type
Thin
Thick
B type
Thin
Thick
C type
Thin
D type
Thick
Thin
1.5
0.5
1.0
1.0
0.5
Group A
(SULPHIDE)
(Thin)
1.5
Group B
(ALUMINA)
(Thin)
0.5
Group C
(SILICATE)
(Thin)
-
Thick
Group D
(OXIDE)
(Thin)
1.0
To confirm that the inclusions are of sulphide type, SEM-EDS analysis was also carried out.
(a)
(b)
Fig. 4.3: (a) SEM image of inclusion in Heat ID 1 at 799X magnification (b)EDS spectrum
of point 3 shown in image
48
SEM-EDS analysis confirms the results of inclusion rating and reveals that the inclusions
are Manganese Sulphide (MnS) stringers.
The control of sulphur and its associated level of sulphide inclusions in rail steel is a
challenge in spite of RH-degassing. This can be attributed to the silicon killing practice
adopted in rail steels and RH-degassers limitations for desulphurization understanding the
effect of secondary refining parameters on desulphurization and inclusion removal.
49
50
CONCLUSION
51
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, steel cleanliness
improvements were achieved.
FUTURE WORK
Correlate the development of inclusion composition and count in the furnace,
ladle, tundish and mold slags with inclusions found at each respective steelmaking
vessel.
Aluminium oxide precipitates are formed during fast cooling of the liquid steel. The
question arises whether these precipitates may act as nuclei for iron solidification
and thus enable control of the steel microstructure in certain (future) conditions.
Development of automatic/online inclusion behavior and assessment technology
during processing and production of steel
52
REFERENCES
53
REFERENCES
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[3]
[4]
H.A. Sloman and E.L. Evans, JISI, 1951, vol. 169, pp. 145-152
[6]
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
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Ototani, Calcium Clean Steel, Springer-Verlag, New York, 1986, pp. 2-9.
[11]
Tupkary R.H.: Introduction To Modern Steel Making Khanna Publisher, Delhi 7th
54
Chart II for quantitative measurements, Clean Steel 3 Conference Proceedings, The Institute
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55