Characterization of Inclusions in Calcium Treated Steel

REPORT SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE

Of

MASTER OF TECHNOLOGY
In

METALLURGICAL AND MATERIALS ENGINEERING

Submitted by
BHARAT KHURANA
(13MT30029)

UNDER THE GUIDANCE OF

Prof. Gour Gopal Roy

DEPARTMENT OF METALLURGICAL AND MATERIALS

ENGINEERING
INDIAN INSTITUTE OF TECHNOLOGY
KHARAGPUR

(APRIL 2018)

1
 Department of Metallurgical and Materials Engineering
Indian Institute of Technology Kharagpur, India
________________________________________________________

CERTIFICATE

The report entitled “Characterization of Inclusions in Calcium Treated Steel” is being

submitted by Mr. Bharat Khurana, Roll No. 13MT30029, to the Department of Metallurgical
and Materials Engineering, IIT- Kharagpur for the partial fulfillment of the requirements of the
Degree, Master of Technology in Metallurgical and Materials Engineering from Indian
Institute of Technology, Kharagpur. This document is a record of the bona fide work carried
out by him under my supervision and guidance.

This report is, in my opinion, worthy of the standard for which it is submitted.

Date: (Prof. Gour Gopal Roy)

Department of Metallurgical and Materials Engineering,

Indian Institute of Technology,
Kharagpur – 721302

2
 AUTHOR’S DECLARATION

I certify that

 The work contained in this report has been done by me under the guidance of my
thesis supervisor.

 The work has not been submitted to any other Institute of awarding any degree or
diploma.

 I have conformed to the norms and guidelines in the Ethical Code of Conduct of
the Institute.

 Whenever I have used materials (Data, theoretical analysis, figure and text) from
other sources, I have given due credit to them by citing them in the text of the
thesis and giving details in the references.

Place: IIT Kharagpur ________________________

Date: Bharat Khurana

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 CONTENTS

1. Acknowledgement 5

2. Abstract 6

3. Introduction 7

4. Literature Review 8

5. Methodology 13

6. Results & Discussions 15

7. Conclusions & Future Scope 26

7. References 27

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 1. ACKNOWLEDGEMENT

With great pleasure I avail this unique opportunity to express my profound sense of gratitude
and indebtedness to Prof. Gour Gopal Roy, Department of Metallurgical and Materials
Engineering, Indian Institute of Technology, Kharagpur, for this efficacious advise, perpetual
and prolific encouragement and constructive criticism during the course of the work and in the
preparation of this project report.

I would like to express my sincere gratitude to all the staff and research scholars of this
department for their help rendered in completion of this project-work.

Place: Kharagpur Bharat Khurana

Date: Department of Metallurgical and Materials Engineering

5
 2. ABSTRACT

Experimental studies have been made on various properties of non-metallic inclusions in steel.
The parameters which have been studied include the modification in inclusion morphology on
calcium treatment, the effect of calcium treatment on the chemical composition of inclusions,
size distribution of inclusions (using both two dimensional and three dimensional
characterization), the agglomeration behaviour of inclusions in conditions prior to the calcium
treatment and after the calcium treatment, kinetics of the calcium treatment and the
enhancement in mechanical properties (including yield strength, ultimate tensile strength and
fatigue behaviour). Samples of steel were obtained from the steel plant in conditions prior to
the calcium treatment and after the calcium treatment. The inclusions for the samples in both
the conditions were isolated using the technique of matrix dissolution. Information about the
morphology of inclusions was obtained by SEM observations. The inclusions isolated from
samples in the calcium treated condition were found to be significantly more circular as
compared to inclusions from the untreated condition. X-ray Computed Tomography was used
to gain understanding about the effect of calcium treatment on average inclusion size and size
distribution of inclusions. For the sample obtained in the untreated condition the fraction of
inclusions in the larger size range was higher while the reverse is true for the sample obtained
in the calcium treated condition. Average inclusion size for the sample in the untreated
condition was 6.116 μm while for the calcium treated sample it was 4.414 μm. Size distribution
of inclusions obtained from SEM images for the two samples indicate similar trends. Studies
were performed on the agglomeration behaviour of inclusions in the two conditions using high
temperature confocal scanning laser microscope (HT-CSLM). Observations were made on the
variation of average inclusion size with time. The increase in the average size due to clustering
of inclusions was significantly more rapid for sample in untreated condition as compared to the
sample in the calcium treated condition. EDS was used to determine the chemical composition
of inclusions. Further, in situ studies were made on the calcium treatment of inclusions in
molten steel and the slowdown in the agglomeration behaviour was quantified. Forces
operative between inclusion particles were measured in both the conditions. The force in the
calcium treated condition was ten times lower as compared to the force in the untreated
condition. This can be explained by modification of inclusion morphology on their calcium
treatment. Tensile tests were performed on the samples in both the conditions. Yield strength
and ultimate tensile strength were found to be significantly higher for the sample in the calcium
treated condition. Low cycle fatigue tests were performed on the samples in two conditions
under identical loading. The number of cycles to failure were found to be significantly higher
for the calcium treated samples. Thus, calcium treatment results in significant improvement in
the mechanical properties of steel.

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 3. INTRODUCTION

There has been an increase in the demand for clean steels for a variety of structural applications
due to their superior mechanical properties and performance properties. Presence of inclusions
in steel is harmful for a variety of reasons. Non-metallic inclusions in steel can cause clogging
of nozzles. Also, their presence results in deterioration in the mechanical properties of steel.
The reason for this is that the inclusions act as sites for stress concentration and hence initiation
of fatigue cracks. During secondary steel making the inclusions are removed by absorption in
the ladle slag. However, it is not possible to remove all the inclusions. Thus, the inclusions are
subjected to calcium treatment by cored wire injection. Prior to the treatment, the inclusions
are composed of alumina in the solid state. After the calcium treatment, the chemical
composition of inclusions gets modified. Calcium aluminate inclusions formed on calcium
treatment are liquid at steel making temperature. They are not likely to cause clogging of
nozzles. Also, these inclusions take up a spherical morphology which are less deleterious as
sites for stress concentration. We have performed studies on the effect of calcium treatment on
the properties of inclusions including their agglomeration behaviour, chemical composition,
morphology, size distribution and effect on mechanical properties of steel.

We have performed experiments to get information about morphology of inclusions in steel

and the effect of calcium treatment on the inclusion morphology. This was done by dissolution
of the ferritic matrix to obtain inclusions in the form of residue which were then studied using
SEM images. Further information about inclusion morphology has been obtained using X-ray
Computed Tomography (XCT). This also helped us to obtain information about the size
distribution of inclusions. The information about size distribution was then compared with that
obtained from SEM images of sections of the steel samples. To understand the chemical
composition of inclusions and the effect of calcium treatment on it EDS detector of SEM was
used. Confocal microscopy was used to get information about agglomeration behaviour of
inclusions and the slowdown in clustering on calcium treatment. This was performed using two
different samples, in conditions prior to the calcium treatment and after the calcium treatment.
Further, in situ studies were performed on calcium treatment of inclusions using a novel
experimental design. Lastly, the effect of inclusion modification on the mechanical properties
of steel was examined.

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 4. LITERATURE REVIEW
Experiments have been performed by Hongbin YIN et al using confocal scanning laser
microscope combined with infrared image furnace to study long range attraction force between
alumina solid inclusion particles which leads to their collision, agglomeration and formation
of clusters. For particles larger than 3 μm in size the magnitude of the force was found to be
10-16 N and the acting length of the force was found to be 10 μm. Collision between particles
led to formation of intermediate aggregates, the collision between these intermediate
aggregates resulted in formation of loose alumina clusters. This was followed by densification
of loose clusters to form compact ones. The origin of the long range attractive force was
explained on the basis of capillary effect around alumina particles on molten steel surface. In
industrial practice, if bubbling/gas injection is used for refining of steel then capillary attraction
force can play an important role to improve collision, agglomeration and cluster formation.

A common method to remove inclusions from molten steel is bubbling. The first reason for
this is that it results in enhancement of collision and agglomeration of inclusions due to the
bath stirring. The second reason is flotation while inclusion particles are in contact with
bubbles. In the work done by Hongbin YIN et al real time observations were made on collision
and agglomeration behaviour of inclusion particles on the surface of steel melts. Interesting
behaviour of the inclusions was revealed and interparticle attraction force was deduced. In the
experiments performed by this group the behaviour of inclusion particles at the surface of
molten steel was observed at a maximum magnification of 2100 and recorded at the rate of 30
frames per second. The minimum size of the inclusion particle on the surface of steel melt that
could be detected was 0.5 μm. The steel sample was machined into a disc 4.3 mm in diameter,
polished to achieve a mirror finish and installed at a focal point of the ellipsoidal chamber of
the furnace. Subsequently, the sample was heated to its melting point by a halogen lamp located
at the other focal point of the chamber as shown in fig. 1. The chemical composition of the
inclusions in steel was identified by EPMA analysis. The inclusions were found to be almost
pure alumina.

As soon as the sample reached molten condition, individual inclusion particles (< 1 μm in size)
and small aggregates (about 2 μm in size) surfaced from the bulk of the melt. The surfaced
aggregates were irregular in shape with sharp tips. The number of particles and aggregates on
the melt surface decreased with time while the average size of the clusters of inclusions
inclusions increased with time. The floating alumina particles were found to attract each other
at a separation far greater than the size of individual particles. If the size difference between
the alumina particles was large then the smaller particle moved in an accelerated manner
towards the larger particle which remained quiescent. On the other hand, for particles of
comparable size the two particles experienced attraction towards each other resulting in a head
on collision. The process of agglomeration of inclusions was summarized as follows:

1. Individual particles and small aggregates undergo collision with each other to form
intermediate sized aggregates.

2. A network of clusters is formed from intermediate sized aggregates.

3. Densification of these clusters results in formation of more compact clusters.

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 Fig. 1: Schematic diagram of confocal scanning laser microscope

As soon as the sample reached molten condition, individual inclusion particles (< 1 μm in size)
and small aggregates (about 2 μm in size) surfaced from the bulk of the melt. The surfaced
aggregates were irregular in shape with sharp tips. The number of particles and aggregates on
the melt surface decreased with time while the average size of the clusters of inclusions
inclusions increased with time. The floating alumina particles were found to attract each other
at a separation far greater than the size of individual particles. If the size difference between
the alumina particles was large then the smaller particle moved in an accelerated manner
towards the larger particle which remained quiescent. On the other hand, for particles of
comparable size the two particles experienced attraction towards each other resulting in a head
on collision. The process of agglomeration of inclusions was summarized as follows:

1. Individual particles and small aggregates undergo collision with each other to form
intermediate sized aggregates.

2. A network of clusters is formed from intermediate sized aggregates.

3. Densification of these clusters results in formation of more compact clusters.

The collision and the agglomeration behaviour was also observed for the solid aluminosilicate
particles. The long range attraction force was found to exist for these particles as well.
However, the magnitude of attractive force operative between these particles was found to be
9
lower. Also, the acting length of the force was shorter. The deformation and densification of
clusters was observed to be much faster for these inclusion particles. It occurred almost
simultaneously with the formation of these clusters. This was attributed to the faster inter-
diffusion across the particle boundaries due to the lower melting point of these inclusions.
However, no such long range attraction force was observed for liquid spherical inclusion
particles.

Characteristics of the long range attraction force operative between the inclusion particles were
investigated in detail. Magnitude and acting length of the force between inclusion particles was
determined. The inclusion particles were approximated to be elliptical discs with dimensions
in two perpendicular dimensions as d1 and d2 and a thickness of 2 μm on the basis of confocal
observations. Further, the particles were assumed to be round discs of radius r given by
(d1d2/4)0.5. Thus, the mass of the particles was approximately determined using the above
measurements. From the measurement of the positions of inclusion particles at intervals of 1/30
s, the acceleration of the inclusion particles were calculated. If one of the particles (with mass
m1) experiences an acceleration towards a larger particle which remains quiescent, the
attractive force between the inclusion particles is given by: F = m1a. Also, if the two particles
in a pair differ significantly in size, the magnitude of the attractive force was found to depend
on the size of the smaller particle in the pair while the acting length was determined by the size
of the larger particle in the pair. Greater is the size of the smaller particle in the pair, greater is
the magnitude of the attractive force operating between inclusion particles. The acting length
of the force increased with the increase in the size of the larger particle in the pair. The effect
of surfactant element on the long range attraction force was found to be negligible.
Composition of the particles was also found to have effect on the magnitude and acting length
of the force operating between inclusion particles. The magnitude and acting length of force
was found to be lower for aluminosilicate particles as compared to alumina particles.

An explanation was provided for the long range attraction force operating between inclusion
particles. A part of the inclusion particles was immersed in molten steel. As a result of this, the
surface of the molten steel at the periphery of the inclusion particles was depressed. When two
such particles came close to each other, the surface of liquid steel between them was even more
depressed. This resulted in imbalance of capillary pressure on the two sides of the inclusion
particles which pushes them towards each other.

Studies have been performed to compare agglomeration characteristics of various types of

particles on the surface of molten steel by Hongbin YIN et al. The solid inclusion particles
were found to experience strong forces of capillary attraction towards each other. These forces
are responsible for their quick agglomeration to form clusters. These forces were also found to
be operative between a pair of particles one out of which is solid and the other is liquid.
However, there was no such force between liquid inclusion particles. Even when two liquid
particles came in touch, merger took place only after contacting for a while. The merger was
found to be even more difficult for smaller particles but was easier for particles of larger size.
These phenomena have been explained in terms of inert gas-oxide inclusion-molten steel three
phase interfacial interaction.

10
In the experiments carried out by Hongbin YIN et al the inclusions that surfaced from High
Strength Low Alloy steel melt were found to have a composition of CaO-60 mass% Al2O3-
SiO2. These inclusions were in liquid state and had a globular shape. They did not collide with
each other and hence agglomeration did not take place for such particles. The average inclusion
size remained unchanged during the experiment. Various kinds of inclusion particles surfaced
from the melt of the Silicon Killed steel. The inclusion particles which were in solid state
collided and agglomerated quickly while the agglomeration of liquid particles took place only
under special conditions. The different types of morphologies for inclusions in solid, liquid or
semi-liquid state are shown in fig. 2. As the morphology of inclusions changes, the depression
of the surface of molten steel between the inclusion particles changes. This explains the
difference in the long range attraction forces between different types of individual particles.

Fig. 2. Depression of liquid steel surface for different inclusion morphologies

Experiments have been performed by Fernandes et al to investigate nonmetallic inclusions in

steel by dissolution of the ferritic matrix. Ferritic matrix was dissolved by the use of
hydrochloric acid and information about the size, morphology and chemical composition of
inclusions was obtained using an SEM with EDS detector. Samples of steel were obtained from
billets in as cast condition and wire rods from rolled billet. SEM images for the residues were
obtained by dissolving the samples obtained from billet in as cast condition and wire rods from
rolled billet. It is evident that isolated inclusions obtained from dissolution of ferritic matrix

11
enable much better determination of inclusion size, geometry and composition. This may be
attributed to the fact that in the conventional metallographic method, the inclusions stay
countersunk in the steel matrix and cannot be completely observed leading to imprecise
conclusions. Moreover, the smallest possible diameter of the electron beam in the region to be
analyzed can be 2 μm. If the chemical composition of inclusions within a steel matrix smaller
than this size is to be determined the results will be affected by the chemical elements in the
steel matrix. However, no such interference is likely to take place in case of isolated inclusions.
We have used a similar method to study the effect of calcium treatment on morphology of non-
metallic inclusions in steel. (As discussed in subsequent sections).

Fig. 3. Procedure for study of non-metallic inclusions by matrix dissolution to obtain residue

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 5. METHODOLOGY

Samples of steel were obtained from ladle furnace in TATA steel plant (Jamshedpur) for two
different conditions - prior to calcium treatment and after the calcium treatment. For both the
conditions, a part of the sample (weighing about 10 g) was used to obtain the isolated
inclusions. Using coarse SiC paper, the sample surface was grinded to remove oxides and dirt.
This was followed by washing the sample using ultrasonic agitation and acetone to remove
possible dirt from the surface. The sample was dried with hot air flow and weighed. The sample
to be dissolved was placed in a beaker with 160 ml of an aqueous solution of HCl at a
temperature range of 80–100 °C. The steel sample was completely dissolved after about 1.5
hours. The solution was filtered and the residues obtained on the filter paper were dried using
an oven. SEM images were obtained for isolated inclusions from the two samples.

Samples of aluminum killed steel were obtained from ladle furnace in Vishakhapatnam Steel
Plant. Composition of sample (in weight %) collected prior to calcium treatment was 0.16 %
C, 0.67 % Mn, 0.011 % P, 0.012 % S, 0.23 % Si and 0.027 % Al and for sample collected after
calcium treatment it was 0.16 % C, 0.67 % Mn, 0.011 % P, 0.012 % S, 0.23 % Si, 0.027 % Al
and 0.0022 % Ca. SEM studies were performed to obtain information about size distribution
of inclusions in two samples. Inclusions were observed using secondary electron images.
Dimension of individual inclusions was measured in two directions perpendicular to each other
and average of the two lengths was taken as the size of inclusion. Three dimensional
characterization of inclusions in the two samples was obtained using XCT studies. X-ray
computed tomography (XCT) measurements were performed using the Zeiss Versa 520
system. This enabled non-destructive 3D observation of the sample and quantification of the
inclusions in it. The sample was placed on a rotating turntable between the X-ray source and
detector. As X-rays pass through the sample, they are either attenuated or pass through the
sample resulting in a grey-scale radiograph on the detector screen. The resolution of the scan
was determined by the magnification factor of the object that results from the relative position
of the source/detector geometry. Numerous radiographic projections were taken through a full
360° rotation that was then back projected to reconstruct the 3D volume. This volume consists
of an array of 3D pixels called voxels with an associated grey value between 0 and 65535
proportional to the relative attenuation of the X-rays by the material. The source and detector
were positioned to achieve the maximum magnification while remaining within the field of
view. Alongside geometric magnification, the Zeiss scanner had a number of optics to achieve
additional magnification where the 4× objective was utilized in this study. The combination of
the above resulted in a 1.6 μm resolution. For XCT measurements, samples with a dimension
of 1 mm × 1 mm × 5 mm were cut from the parent samples and subsequently polished and
cleaned by acetone. Information regarding the size distribution of inclusions and average
inclusion size obtained from these studies was compared with that obtained from SEM studies.
EDS was used to obtain information regarding chemical composition of inclusions in the two
samples.

For observation of the agglomeration behaviour of inclusions High Temperature – Confocal

Scanning Laser Microscope was used. Samples of aluminum killed steel prior to calcium
treatment and after calcium treatment were machined into cubes of 2 mm. The sample collected
13
in condition prior to calcium treatment was first placed inside an alumina crucible, contained
within a Pt crucible and lid. Thereafter, it was placed on an alumina spacer to prevent sticking
to the Pt sample stage. Fig. 4 shows the sample set-up used in HT-CSLM. The experimental
chamber was evacuated and refilled with argon (<2 ppm O2) three times to remove any
impurities from sample surface. The sample was heated to a calibrated temperature of 1873 K
(1600 °C) under argon gas. The argon gas was then switched off so that the surface became
still to observe the sample. A similar procedure was used to observe the clustering behaviour
of inclusions for sample collected after calcium treatment.

Fig. 4. Schematic for confocal setup

Measurements were performed on the mechanical properties of steel in conditions prior to the
calcium treatment and after the calcium treatment. Miniature samples were prepared to perform
the tensile tests and the fatigue tests. The diameter of the samples at the grip section was 5 mm
and the gage length was in the form of a circular arc. The minimum diameter in the gage length
was 3.33 mm. A gage length of 20 mm was used while the length of the grip sections on the
either side was 15 mm. Tensile test was performed on the samples in both the conditions - prior
to the calcium treatment and after the calcium treatment. The test was performed on two
samples for each condition. The values of percentage elongation, yield strength and ultimate
tensile strength were obtained from the tensile test data. Further, low cycle fatigue tests were
performed on the samples in both the conditions with identical value of stress amplitude. The
value of mean stress was kept at zero and a frequency of 8 hertz was used for the test. The
number of cycles to failure was observed for each sample. An average of three measurements
was used for the material in each condition. A comparison was made between the values of
yield strength, ultimate tensile strength and number of cycles to failure for the two conditions.

14
 6. RESULTS AND DISCUSSIONS
Fig. 5 and fig. 6 show the images obtained for isolated inclusions from the non-treated sample
and calcium treated sample respectively. It can be seen that a much better observation of
inclusion morphology is possible using this technique. When the inclusions are within the
matrix a part of them is submerged in steel. This hinders determination of their size and
morphology with certainty. It is clear that calcium treatment results in formation of inclusions
which are much more circular as compared to the ones in non-treated condition.

Fig. 7 a and b show the X-ray Computed Tomograph for non-treated sample and calcium
treated sample respectively. These tomographs were used to find the size distribution
ofinclusions for the two samples. Fig. 8 a shows the size distribution of inclusions for samples
collected from ladle furnace before and after calcium treatment. The size distribution for
inclusions larger than 9 µm has been shown separately in fig. 8 b for greater clarity. As can be
seen from fig. 8 a, for sample of calcium treated steel the fraction of inclusions in size range
0.0-3.0 µm and 3.0-6.0 µm are both greater than 0.4. For the sample of non-treated steel the
fraction of inclusions in size range 0.0-3.0 µm and 3.0-6.0 µm are both less than 0.3. However,
for the calcium treated steel fraction of inclusions in size range 6.0-9.0 µm is less than 0.15,
while for the non-treated steel fraction of inclusions in size range 6.0-9.0 µm is about 0.25.

Fraction of inclusions in the smaller size range is higher for calcium treated steel and the
fraction of inclusions in the larger size range is higher for non-treated steel. For calcium treated
steel average inclusion size is 4.414 µm while for non-treated steel it is 6.116 µm. The shift in
the size distribution of inclusions is due to difference in agglomeration behavior of inclusions
in calcium treated steel and non-treated steel. Prior to calcium treatment, the inclusions in steel
are primarily composed of alumina which is formed due to the reaction of aluminum with
oxygen during aluminum killing of steel. Alumina inclusions which are solid at steel making
temperature of about 1600oC take the shape of disc on the inert gas/molten steel interface and
the angle of contact at the interface between alumina inclusions and molten steel is 133o. When
two such alumina inclusions come close to each other, there is a depression of inert gas/molten
steel interface between them. This results in a difference in pressure on two sides of inclusion
particle because of molten steel on one side and inert gas on the other side. This pushes the
inclusion particles towards each other resulting in their agglomeration to form larger clusters.
This leads to an increase in average inclusion size for the non-treated steel.

Fig. 5. SEM images for isolated inclusions from non-treated sample

15
 Fig. 6. SEM images for isolated inclusions from calcium treated sample

a) b)

Fig. 7. X-ray Computed Tomograph showing inclusion particles for a) Non-treated and b) Calcium treated steel
samples

However, after calcium treatment, calcium aluminate inclusions are formed. Their composition
as determined using an SEM-EDS indicates that they are liquid/semi-liquid at 1873 K
(1600oC). These inclusions take the shape of lens like particles on the inert gas/molten steel
interface. The depression of inert gas/molten steel interface when such lens like particles come
close to each other is much lesser, resulting in a significantly weaker force of attraction. Hence
the tendency for agglomeration is much lower for inclusions in calcium treated steel resulting
in lower inclusion size. However, a small fraction of inclusions in calcium treated steel are
found to lie in the size range 30-33 µm. This is due to alumina inclusions which nucleate prior
to calcium treatment and get a long duration to agglomerate and form large inclusion clusters.

16
 a) b)

Fig. 8. a) Size distribution of inclusions obtained from XCT b) Size distribution for size > 9 µm

a) b)

Fig. 9. a) Size distribution of inclusions obtained from SEM b) Size distribution for size > 2 µm

Fig. 9 a shows the size distribution of inclusions as obtained from SEM images. Size
distribution of inclusions greater than 2 µm in size has been shown separately in fig. 9 b for
greater clarity. Size distribution achieved from SEM images follows a trend similar to that
obtained from XCT analysis; for smaller size range calcium treated steel has higher fraction of
inclusions while for larger size range fraction of inclusions is higher for non-treated steel. Fig.
10 a and b shows the SEM-EDS maps for non-treated steel and calcium treated steel. Maps for
calcium treated steel indicate significant enrichment in calcium along with formation of a
sulphide ring as compared to non-treated steel.

Fig. 11 shows the variation in average inclusion size with time as observed using confocal
microscopy. Prior to calcium treatment the increase in average inclusion size is quite rapid
from 2.3 µm to 7.8 µm in 5 min. However, after calcium treatment the increase in average
inclusion size is significantly slowed down. For the same holding duration of 5 min the increase
in average inclusion size is from 1.8 µm to 3.4 µm. This slowdown of the rate of increase in
average inclusion size is related to slower clustering of inclusions in condition after calcium
treatment. Ternary phase diagram for the CaO-Al2O3-SiO2 system constructed using
17
FACTSAGE for steel making temperature (1600 °C) is shown in fig. 12. It can be seen that
calcium treatment results in a change in physical state of inclusions from solid to liquid / semi
- liquid. The solid alumina inclusions prior to calcium treatment exert strong capillary forces
on each other resulting in much faster clustering as compared to liquid / semi - liquid calcium
aluminate inclusions.

a)

b)

Fig. 10. SEM-EDS maps for a) non-treated steel b) calcium treated steel

18
 Fig. 11. Variation of average inclusion size with time of holding during confocal microscopy for non-treated
sample and for sample taken one minute after calcium treatment

Fig. 12. Ternary phase diagram constructed using FACTSAGE

Study on in situ observation of calcium treatment of inclusions in aluminum killed steel

using confocal microscopy

The in-situ experiment is designed in such a way that it is possible to heat the sample to a
particular temperature and melt it partially while keeping the core solid which enables us to
observe the agglomeration behaviour of inclusions before reaction with CaO takes place. Later,
19
this is followed by an increase in temperature so that the sample is fully molten and inclusions
react with CaO. The fraction of sample melted at different temperatures was calibrated and the
direction of melting was deduced by heating dummy samples of identical dimensions to
different temperatures (1590, 1593, 1596, 1600 and 1603o C) and observing the microstructure
of quenched samples. While three fourth of the sample was molten at a calibrated temperature
of 1600o C, the sample was fully molten at a calibrated temperature of 1603o C. The
experimental chamber was evacuated and refilled with argon (< 2 ppm O2) three times to
remove any adsorbed impurities from sample surface. The sample was heated to a calibrated
temperature of 1600o C under argon gas. The argon gas was then switched off so that the surface
became still, and the sample was observed. After observing the sample for 30 seconds in this
state, the temperature was increased by 3o C to allow complete melting of sample to facilitate
reaction with CaO. Evolution of gas from the sample surface accompanied the reaction.

Fig. 13. Change in inter-inclusion distance with time for a pair of inclusion particles observed a) before calcium
treatment and b) after calcium treatment.

Fig. 14. Variation of Inclusion-size and number of inclusions with holding time during confocal microscopy

20
 Fig. 15. Variation of inter-inclusion distance as a function of time for different pairs of inclusion particles
observed a) 0, 5, 20 and 30 s after melting of sample b) 5, 20, 30 and 60 s after Ca treatment.

Fig. 16. SEM–EDS image and chemical mapping for an inclusion observed in the before treatment material

21
 Fig.17. SEM–EDS image and chemical mapping for an inclusion observed on the surface of the sample after
calcium treatment

Fig. 18 and fig. 19 show the tensile test curves for two specimens in the condition prior to
calcium treatment. Fig. 20 and fig. 21 show the tensile test curves for two specimens in the
condition after the calcium treatment. Average value of yield strength for the specimens in the
condition prior to calcium treatment is 405 MPa while the average value of yield strength for
the specimens in the condition after the calcium treatment is 486 MPa. Average value of
ultimate tensile strength for the specimens in the condition prior to calcium treatment is 605
MPa while the average value of ultimate tensile strength for the specimens in the condition
after the calcium treatment is 765 MPa. Fatigue tests were performed on the specimens of
materials in both the conditions using an identical value of stress amplitude of 370 MPa and
mean stress of 0 MPa. On an average the number of cycles till failure for the specimens in the
before treatment condition is 1590 while for the specimens in the calcium treated condition it
is 2250 cycles. Fig. 22 and fig. 23 show fractographs obtained using SEM for the samples in
the conditions prior to calcium treatment and after calcium treatment respectively. The
significant improvement in mechanical properties of steel on calcium treatment can be
attributed to modification in inclusion morphology.

22
Fig. 18. Tensile test for before treatment condition (specimen 1)

Fig. 19. Tensile test for before treatment condition (specimen 2)

23
Fig. 20. Tensile test for after treatment condition (specimen 1)

Fig. 21. Tensile test for after treatment condition (specimen 2)

24
Fig. 22. Fractograph obtained from SEM from the sample in before treatment condition

Fig. 23. Fractograph obtained from SEM from the sample in after treatment condition

Fig. 24. Number of cycles till failure for the non-treated sample and the
calcium treated sample

25
 7. CONCLUSIONS & FUTURE SCOPE
From the inclusions isolated using dissolution of ferritic matrix it can be observed that calcium
treatment results in formation of much more circular inclusions. XCT and SEM observations
indicate a lower average inclusion size for calcium treated sample as compared to before treated
sample.
During observation of the agglomeration behaviour of inclusions using two different samples
(one in untreated condition and the other after calcium treatment) it was found that the increase
in average inclusion size due to cluster formation is significantly slowed down in the condition
after calcium treatment. In the condition prior to the calcium treatment, there was an increase
in average inclusion size from 2.3 μm to 7.8 μm in 5 min. However, after the Ca treatment the
increase in average inclusion size in the same duration was from 1.8 μm to 3.4 μm.
The findings for the in situ study are as follows:
• It was observed that prior to calcium treatment, average inclusion size increased due to
clustering from 6.17 µm to 35.97 µm in 30 s but after calcium treatment it increased only
slightly from 10.1 µm to 13.67 µm even after a holding time of 60 s.
• Results show that for same initial inter-inclusion distance of about 40 µm, a pair of inclusion
particles before calcium treatment took 2.6 s to come together while a pair of inclusion particles
after calcium treatment took more than 8 s to come together.
• From the present study, it can be concluded that after calcium treatment, magnitude and
acting length of force responsible for agglomeration of inclusions reduced causing a delay in
the collision and clustering of inclusion particles as compared to before treatment.
Improvement in mechanical properties of steel due to modification of inclusion morphology
on calcium treatment was quantified as follows:
 Average value of yield strength for the specimens in the condition prior to calcium
treatment is 405 MPa while the average value of yield strength for the specimens in the
condition after the calcium treatment is 486 MPa.

 Average value of ultimate tensile strength for the specimens in the condition prior to
calcium treatment is 605 MPa while the average value of ultimate tensile strength for the
specimens in the condition after the calcium treatment is 765 MPa.

 On an average the number of cycles till failure for the specimens in the before treatment
condition is 1590 while for the specimens in the calcium treated condition it is 2250 cycles
(under identical conditions).
More experiments need to be performed for determination of the effect of calcium treatment of
inclusions on the mechanical properties of steel. This includes performing the tensile tests for
determination of yield strength and ultimate tensile strength in the untreated condition and
calcium treated condition. Also, fatigue properties of the material in both the conditions need
to be investigated in greater detail. Number of cycles to failure can be measured at different
values of mean stress. This can be used to prepare an S-N curve. Effect of calcium treatment
on the fatigue crack growth rate needs to be determined. The fractured surface can be observed
using SEM images.

26
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