Efecto Del Boro en El Grafito Paper

On the Inoculation and Graphite Morphologies of
Cast Iron
Haji Muhammad Muhmond
Doctoral Thesis
Stockholm, Sweden 2014
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PREFACE
The work described in this doctoral thesis has been carried out at the Department of Materials
Science and Engineering, The Royal Institute of Technology (KTH), between Januray 2011 to
November 2014. The work was initiated by Prof. Hasse Fredriksson, as my supervisor. By the
combined effort of Prof. Hasse Frediksson (KTH) and Lena Magnusson (Elkem), this work got
a full economical support from Elkem Foundry and Technology (Kristiansand Norway). Elkem
Foundry and Technology is producing various types of inoculants for cast iron production. The
research was therefore intended to study the inoculation mechanism and its effect on the
graphite growth morphology. Most of the experimental work has been performed at metallurgy
labs., in the materials science and engineering department (KTH), while some microscopic
analysis as HRTEM, Ion Etching and polishing, and FIB sampling was performed at Swerea
Kimab, Electrum Lab, Stockholm University and in KTH, Stockholm, Sweden.
This doctoral thesis is based on the following supplements.
Supplement 1:
Relationship between Inoculants and the Morphologies of MnS and Graphite in Gray Cast Iron
H. M. Muhmond and H. Fredriksson
Metallurgical and Materials Transactions: Volume 44b, April 2013—283
Supplement 2:
An Investigation on the Effect of S and Al on the Austenite Growth Morphology in Gray Cast
Iron, Using Thermal Analysis and Etching Technique
Transactions of Indian Institute of Metallurgy Volume 66(2), April 2013—192
Supplement 3:
Graphite Growth Morphologies in Cast Iron
Sixth International Conference on Solidification and Gravity, September 2-5, 2013, Miskolc-
Lillafüred, Hungary, published in Materials Science Forum, Vols. 790-791 (2014) pp 458-463
Supplement 4:
Relationship between the Trace Elements and Graphite Growth Morphologies in Cast Iron
Metallurgical and Materials Transactions A, Volume 45, Issue 13, pp 6187-6199
Supplement 5:
Graphite Growth Control in Nodular Cast Iron
Supplement 6:
Graphite Growth Morphologies in High Al Cast Iron
Accepted for publication in the proceedings ‘Advances in the Science and Engineering of
Casting Solidification’: An MPMD Symposium Honouring Doru Michael Stefanescu,
Florida USA, 15 March 2015)
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The Author’s contribution to the different supplements of this thesis
Supplement 1: Literature servey, preparing alloys, preparing experimental setup, experimental
planning, performing experiments, preparing samples, microstructural analysis by using light
optical microscope, SEM, EDX and major parts of thermodynamic analysis and writing.

planning, performing experiments, using DSC furnace, DSC calibration, preparing samples,
and microstructural analysis by using light optical microscope, SEM, colour etching, using
ThermoCalc database and major parts of writing.

planning, performing experiments, Ion etching, preparing samples, and microstructural
analysis by using SEM, FE-SEM. Major parts of writing and thermodynamic calculations.

planning, performing experiments, thermal analysis and calibration, deep etching and
microstructural analysis by using SEM, FE-SEM. Analysis on HRTEM images and graphene
bonding modelling and major parts of writing.

planning, performing experiments, deep etching, preparing samples, microstructural analysis
by using SEM. Thermodynamic calculations and major parts of writing.

planning, performing experiments, deep etching, preparing samples, microstructural analysis
by using SEM. Thermodynamic calculations and major parts of writing.
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ABSTRACT
Research was conducted to understand the nucleation mechanism of graphite flakes and
nodules and the effect of various elements on the growth morphology of graphite.
Investigations were started on flake graphite cast iron. The effect of S on the graphite
morphology and MnS was experimentally analysed. The influence of various type of oxides on
the growth morphology of MnS and their relation with the graphite growth morphology was
studied carefully through series of experiments, and results were related to the thermodynamic
calculations, performed to predict the nucleation of oxides and sulfides at any temperature. The
calculations were supported by EDX analysis on particles in the samples, showing sequential
nucleation of flake graphite. The austenite volume fraction and the dendrite growth orientations
were affected by the addition of Al to the melt. The effect of aluminium oxide and sulfur was
studied on the austenite growth morphology with the help of colour etching technique. Thermal
analyses were performed to study the effect of sulfur content on austenite volume fraction and
growth morphology using DSC. The latent heat of solidification and the rate of austenite
formation was studied and related to the sulfur content in the alloy.
To study the effect of O and S on the graphite morphology, pure Fe-C alloy was prepared and
strong de-oxidizers and de-sulfurizer (Mg, Ca and Sr) were tested. With the help of ion etching
and polishing, we were able to reveal the graphite growth morphology. The morphological
changes in the graphite were explained by relating it to the composition of the melt in regard
of dissolved S and O in the melt. The effect of other trace elements such as S, F, O, N, P, B
and Se, was also investigated by testing them on an ultra-pure Fe-C alloy. The possibility of
substituting a foreign atom in the basal plane of graphite was analysed based on the bonding
energy between C and the foreign atoms. The resulting change in the structure of the basal
plane was studied using Avogadro software and the resulting model were compared with the
experimental results. The basal plane of nodular, flake and undercooled graphite was studied
with the help of HRTEM, which showed differences in the lattice spacing between different
graphite morphologies. The latent heat measurement showed that flake graphite have higher
energy than the undercooled or vermicular graphite. This research made us enabled to tell about
the growth along c-plane in graphite and the reason behind the transition of graphite
morphology.
The effect of inoculation temperature and inoculation sequence on the nodularity was studied.
EDX analysis were performed and the results were compared to the thermodynamic
calculations. It was found that, the melt composition is controlling the graphite growth
morphologies. Strong de-oxidizers and de-sulfurizer are necessary to reduce O and S to a level
where it does not influence the graphite growth morphology. The effect of various elements on
the activity of oxygen in the melt is calculated. High Al cast iron was also studied. The major
problem associated with this type of alloy was that, the Mg was not effective in producing
nodular graphite. Experiments showed that de-oxidizers stronger than Mg are required to
increase the nodularity. Thermodynamic calculations showed that the activity of oxygen in the
melt was changing strongly by increasing the Al content in the alloy. This was increasing the
required oxygen level to nucleate MgO.
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Keywords. Cast iron, nucleation, graphite growth morphology, graphene, EDX,
Thermodynamics, oxides, sulfides, transition, nodular graphite, flake graphite.
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ACKNOWLEDGMENT
This research was performed with Professor Hasse Fredriksson as my thesis supervisor. During
the course of the work, he has been very patient and helpful. He provided me the best guidance
and motivated me at every moment. He was fascinated every time by the results and the delight
on his face gave me more energy to work more and explore something more. I could not have
been able to be in this state of knowledge without him. I am very grateful for his interest and
active role in this research.
I am thankful to Dr Lena Magnusson who played an important role in arranging the financial
support from Elkem Foundry and Technology-Norway. She has been very helpful for me in
writing scientific papers. I want to thank Elkem for providing me the opportunity to work on
this project.
I also want to thank my friends for keeping the work environment alive and the energy which
motivated me to work in a pleasant environment.
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Dedicated to my Parents, without whom everlasting good wishes and
prayers, I would not have been able to be in this stage of life. God
Bless their soul!
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CONTENTS
PREFACE .......................................................................................................................................................... 2
ABSTRACT ........................................................................................................................................................ 4
ACKNOWLEDGMENT ........................................................................................................................................ 6
CHAPTER I ...................................................................................................................................................... 11
GENERAL INTRODUCTION .............................................................................................................................. 11
1.1 HISTORY .................................................................................................................................................... 11
1.2 DIFFERENT TYPES OF CAST IRON ...................................................................................................................... 11
1.3 THEORIES ABOUT GRAPHITE NUCLEATION ......................................................................................................... 12
1.3.1 The graphite theory ...................................................................................................................... 12
1.3.2 The Gas Bubble Theory ................................................................................................................. 12
1.3.3 The Salt-Like Carbide Theory ......................................................................................................... 12
1.3.4 The Silicon Carbide Theory ............................................................................................................ 12
1.3.5 The oxide/sulfides theory .............................................................................................................. 12
1.4. INOCULATION ............................................................................................................................................. 13
1.5. ALLOYING AND TRACE ELEMENTS .................................................................................................................... 14
1.6 INTRODUCTION TO CURRENT WORK ................................................................................................................. 15
1.6.1 The effect of MnS and Oxides on Graphite Morphology ............................................................... 15
1.6.2 Austenite Growth Morphology and Latent Heat .......................................................................... 15
1.6.3 The Effect of Trace Element on the Transition of Graphite Growth Morphologies ....................... 16
1.6.4 Graphite Growth Control .............................................................................................................. 16
1.6.5 High Al cast iron ............................................................................................................................ 18
CHAPTER 2 ..................................................................................................................................................... 19
MATERIALS AND EXPERIMENTAL METHODOLOGY......................................................................................... 19
2.1 THE EFFECT OF MNS AND OXIDES ON GRAPHITE MORPHOLOGY ........................................................................... 19
2.2 AUSTENITE GROWTH MORPHOLOGY AND LATENT HEAT ..................................................................................... 20
2.3 GRAPHITE GROWTH MORPHOLOGIES .............................................................................................................. 21
2.4 EFFECT OF TRACE ELEMENTS ON THE TRANSITION OF GRAPHITE GROWTH MORPHOLOGY ............................................ 21
2.6 HIGH AL CAST IRON...................................................................................................................................... 23
CHAPTER 3 ..................................................................................................................................................... 24
RESULTS ......................................................................................................................................................... 24
3.1. THE EFFECT OF MNS AND OXIDES ON GRAPHITE MORPHOLOGY ............................................................................. 24
3.1.1. EDX analysis ...................................................................................................................................... 24
3.1.2. Effect of sulfur content and inoculation on MnS growth morphology .............................................. 24
3.1.3. Effect of sulfur content and inoculationo on the graphite growth morphology............................... 26
3.2. AUSTENITE GROWTH MORPHOLOGY AND LATENT HEAT ....................................................................................... 29
3.3. GRAPHITE GROWTH MORPHOLOGIES .................................................................................................................. 32
3.3.1. De-oxidation of the melt using pure Mg. .......................................................................................... 32
3.3.2. De-oxidation of the melt using pure Ca. ............................................................................................ 33
3.3.3. De-oxidation of the melt using pure Sr .............................................................................................. 35
3.3.4. Star like growth mechanism in the nodular graphite ........................................................................ 35
3.4. THE EFFECT OF TRACE ELEMENTS ON THE TRANSITION OF GRAPHITE GROWTH MORPHOLOGIES ....................................... 37
3.4.1. Effect of S, F, O, P, N, B and Se on graphite morphology .................................................................. 37
3.4.2. HRTEM study of spheroidal, flake and fine undercooled graphite .................................................... 37
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3.4.3. Latent heat measurement ................................................................................................................. 38
3.5. GRAPHITE GROWTH CONTROL IN NODULAR CAST IRON ........................................................................................... 40
3.6. HIGH AL CAST IRON ........................................................................................................................................ 42
CHAPTER 4 ..................................................................................................................................................... 43
4. DISCUSSION .......................................................................................................................................... 43
4.1. RELATIONSHIP BETWEEN INOCULANTS AND MNS IN GRAY CAST IRON ..................................................................... 43
4.2. EFFECT OF S AND AL ON THE AUSTENITE GROWTH MORPHOLOGY AND LATENT HEAT MEASUREMENT............................ 46
4.3. GRAPHITE GROWTH MORPHOLOGIES .............................................................................................................. 49
4.4. RELATIONSHIP BETWEEN THE TRACE ELEMENTS AND GRAPHITE GROWTH MORPHOLOGIES .......................................... 51
4.4.1. Graphite crystallization ................................................................................................................. 58
4.5. GRAPHITE GROWTH CONTROL IN NODULAR CAST IRON ........................................................................................ 59
4.5.1. Thermodynamics of inoculants ..................................................................................................... 62
4.5.2. The effect of inoculants on the activity of oxygen with MgO ....................................................... 63
4.5.3. The formation of complex compounds and oxygen level .............................................................. 64
.................................................................................................................................................................... 65
4.6. GRAPHITE GROWTH MORPHOLOGIES IN HIGH AL CAST IRON: SIAL ......................................................................... 68
CHAPTER 5 ..................................................................................................................................................... 70
CONCLUDING DISCUSSION ............................................................................................................................. 70
BIBLIOGRAPHY ............................................................................................................................................... 72
SUPPLEMENT 1 ........................................................................................... ERROR! BOOKMARK NOT DEFINED.
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CHAPTER I
GENERAL INTRODUCTION
1.1 History
Cast iron was invented in China in the 5th century BC [1]. They used to make pots and weapons.
It was more desirable because it was cheaper. In the west it became available in the 15th century
and the first usage to make cannon and shot. Henry VIII initiated the casting of cannons in
England by using blast furnaces. These were heavier and cheaper which enabled England to
arm her navy better. In 1712 steam engine was developed with cast iron by Thomas Newcomen.
In the late 1770s cast iron usage began for structural purposes. Since then it has been used for
numerous applications which continues even today. Most of its use is in the heavy construction
and in the car, truck industry.
1.2 Different types of cast iron
Cast iron can be hypo eutectic with primary phase as austenite and hyper eutectic with primary
phase as graphite. Based on the graphite structure, there are several types of cast iron. The
major two types can be gray iron with flake graphite and ductile iron, with nodular or spheroidal
graphite (Fig. 1). There is an intermediate type which is called compacted graphite which
contains a fraction of nodular graphite and the remaining graphite is in irregular shape with
undefined geometry.
Gray Iron: Uniformly distributed Gray Iron: fine Undercooled Gray Iron: Inter-dendritic
Graphite flakes and coarse flakes of graphite graphite flakes
Ductile Cast Iron: Compacted Cast Iron:

High nodularity Low nodularity
Figure 1: Different types of Cast Iron
Now a day’s high Si cast iron became popular due to their high strength. The graphite
morphology can be either nodular or a combination with chunky/vermicular type of graphite.
High Si together with Mo alloys are also used which are called SiMo cast iron. Another alloy
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SiAl which contains both relatively low Si and high Al content, is in use which offers good
properties in wear resistance and high temperature performance. The shape and size of graphite
influences mechanical, thermal and various other properties.
1.3 Theories about graphite nucleation
Cast iron is a composite of graphite with the iron matrix. The nucleation of graphite in cast iron
has been debated over many decades and many theories have been presented. A short
introduction will be provided about those theories in the following.
1.3.1 The graphite theory
According to Boyles (1947 [2], graphite grows from already present small sizes crystalline
graphite in the melt. Eash [3] presented the idea of Si rich regions around the dissolving
graphite particles, when the melt is treated with Si based inoculants. The solubility of C is
sufficiently low in those regions which can promote the precipitation of graphite, but Feest et.
al [4] showed that the dissolution time of ferrosilicon in liquid iron is a few second and graphite
forms at the interface between dissolving particle and liquid iron. They modified the theory
and proposed that these seed crystal will be preserved in the melt provided that Ba or Sr is
present in sufficient amounts to prevent the graphite from dissolving back into the melt.
1.3.2 The Gas Bubble Theory
Karasy [5] presented this theory in 1976. According to him, graphite can only crystallize if it
is protected by some boundary such as the gas bubble of Co and the graphite will grow in this
bubble. However it is not possible to grow a full graphite into the bubble as carbon cannot
diffuse into the solid of grown graphite.
1.3.3 The Salt-Like Carbide Theory
Lux [1964] [6] considered both homogeneous and heterogeneous nucleation of graphite.
According to him certain elements like Ca, Sr and Ba forms salt like carbides in the liquid
which offers a close match of lattice parameters to graphite and reduces the interfacial energy
between the nucleus and the substrate to allow for extensive graphite nucleation during
solidification.
1.3.4 The Silicon Carbide Theory
Following the dissolution of ferrosilicon in liquid cast iron, Wang and Fredriksson (1981-1984)
[7, 8] observed that SiC crystals and graphite particles were formed in the melt close to the
dissolving ferrosilicon particles. A theory was developed and calculations were performed to
explain the nucleation of graphite and the fading mechanism of these particles. The theory was
based on the assumption of the existence of local supersaturation of C and Si in the melt
subsequent to the SiC dissolution which provides the necessary driving force for homogeneous
nucleation of graphite. The fading effect was explained by the homogenization of C and Si in
the melt through convection and diffusion.
1.3.5 The oxide/sulfides theory
Non-metallic and metallic inclusions play an important role in precipitating oxides, sulfides
and nitride particles. Kusakawa (1988) [9] reported that non-metallic inclusions show the
highest inoculation effect. He believes that oxides, especially silica acts as a nucleus for
graphite. The technique of X-ray microanalysis and electron diffraction pattern were used in
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identifying the nucleating particles. Several other researchers have suggested the growth of
graphite on sulfides, oxides and nitrides ((Gadd [10]; Jacobs, [11]; Muzmudar [12, 13] etc).
Warrick [14] suggests that nuclei for flake graphite and spheroid are composed of complex
oxides and sulphides. Also Skaland [15] reported that oxy-sulfide particles will have a at least
one lattice spacing that could match the graphite lattice spacing and creates the possibility of a
favoured substrate for graphite growth. Igarashi et. al [16] found MgO/MgS enveloped by
(Mg,Si,Al)N, nucleating a nodule. Also he observed CaS, MgO and Al2O3 in the core while
(Al,Mg,Si)N in the shell surrounded by graphite nodule. In another article Igarashi et. al [17]
reported the formation of FeClx+(Mg,Al,Si)xOx particle in the core of a graphite nodule in high
purity cast iron. Nakae et. al [18] made analysis on different spheroids and reported that the
formation mechanism of SG is not based on the nuclei. He found different types of compounds
as nuclei for spheroids such as (Mg,Si, Al)N-oxides, (La,Ce,Nd)OxSy, FeClx, (Ce,La,Nd)S and
SiO2 as core compounds. Campbell [19] gives us the concept of oxide bifilm in the melt floating
in the undercooled region. The sulfides are said to form a shell around the oxide particles and
then the graphite nucleates the particle sitting on the bifilm and follows its growth over the
sulfide layer until it constitutes a flake of graphite.
The most commonly observed oxides which are playing a role in graphite nucleation are Al2O3,
BaO, CaO, Ce2O3, La2O3, MgO, SrO, SiO2 and MgO. Sulfides which have been observed in
connection to graphite are CaS, CeS, BaS, MgS, MnS, Mo2S. There are few nitrides which can
be formed such as TiN, AlN and MgN. However the efficiency of nucleation of graphite is
greater on oxides than on sulfides and nitrides. Beside pure oxides, there have been observed
complex oxides as well such as MgO. SiO2, MgO. Al2O3,
MgO.Al2O3.SiO2, CaO.Al2O3, MgO.CaO.SiO2, CaO.Ce2O3. Al2O3.SrO. There are complex
compounds of mixed oxides and sulfide which are found in connection to graphite such as
CaS.Al2O3, MnS.Al2O3, MnS.SrO, MnS.CaO.Al2O3 etc. In alloys having high phosphorus
level, it is possible to form Mg3P2 particles during solidification; however phosphides does not
play a role in the graphite nucleation.
1.4. Inoculation
The process of inoculation is to introduce certain types of micro particles in the melt which
provides nucleation sites for a certain phase; however the purpose of inoculation is to increase
the number of nucleation sites and to modify the size and shape of a phase which is nucleated
upon them. In the case of cast iron these inoculants are some specific elements which are
alloyed with Fe-Si. These elements must have strong affinities towards oxygen and sulfur in
the melt. They result in oxides and sulfides of homogeneous or heterogeneous nature in the
melt and provide nucleation or precipitation sites for graphite. In gray iron relatively low
affinitive elements are used as inoculants such as Al, Sr, Zr and Ca, but Ca is used in small
quantity. Mn is an essential alloying element in gray iron which forms MnS in the melt. In
nodular iron, variety of elements are added in different compositions. Usually those elements
which have the strongest affinities towards oxygen and sulfur are used as inoculants in an
alloyed form with Fe-Si. In nodular iron the sulfur level is much lower than gray iron to avoid
excessive addition of de-sulphurizer. There are a variety of industrially available inoculants
which are used in cast iron according to the desired properties of the materials. A few of them
are introduced below.
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Superseed® inoculants contains 0.5 % Al, 0.1 % Ca, 0.6 to 1 % Sr, 75 % Si and balance iron.
It is widely used for gray iron production, in particular to reduce eutectic carbides in cast iron.
Alinoc® inoculants contains 3.5 to 4.5 % Al, 0.5 to 1.5 % Ca, about 70 % Si and balance Fe.
It can be used in both gray and ductile iron. Reseed® inoculants contains 0.75 to 1.25 % Al,
0.75 to 1.5 % Ca, 1.5 to 2 % Ce, about 73 % of Si and balance iron. It is effective for ductile
iron applications but also could be used in gray iron. Reseed® inoculant promotes good
nodularity in thicker sections. Ultraseed® Ce inoculant contains 0.75 to 1.25 % Al, 1.5 to 2 %
Ce, 0.75 to 1.25 % Ca, less than 1 % S and O, about 73 % Si and balance Fe. This composition
is designed to give highly powerful graphite nucleation in ductile iron and effective chill
reduction. The small amount of O and S coated on the surface is available for reaction with Ca
and Ce during the addition to liquid iron. This inoculant is more effective for ductile iron
production. Ultraseed® Al inoculants contains 3.5 to 4.5 % Al, 0.5 to 1.5 % Ca, <1 % O and
S, about 73 % Si and balance Fe. This inoculant is effective both in gray and ductile iron
production.
Beside the above mentioned inoculants there are many other which are powerful inoculants
such as Superseed® Extra, Barinoc®, Zircinoc®, SMZ®, Ultraseed® Al, Ultraseed® Zr,
Vaxon® and Foundrisil® inoculants.
1.5. Alloying and trace elements
Cast iron is often a complex alloy having many alloying elements and some dissolved elements
as traces. The alloy elements are Si, Al, Mn, Cu, Cr, Mo, Ti, V and Ni. Each alloying element
has its own advantages and disadvantages on the structure. Silicon is used as a strengthening
alloy and also it increases the graphitization of C. Al is in traces in the gray iron and ductile
iron but in SiAl type cast iron it is added in higher amount. Ni refines the pearlite structure,
improves toughness, and evens out hardness differences. Chromium produces free graphite,
chill and it is a powerful carbide stabilizer as well, but it is used in combination with Ni to
reduce carbides. Cu refines graphite, reduces chill and increases fluidity. Mo increase chill and
refines the graphite and pearlite structure. It is often added in conjunction with Ni, Cr and Cu
to form high strength iron. Ti is added to degas the melt from nitrogen but it also increases
fluidity. Mn is to gray iron to form sulfides in the melt which helps in the nucleation of graphite
flakes.
There could be many types of trace elements present in the melt but the most common are S,
O, N, P and halides. In gray iron S level in normally between 0.03 to 0.6 % but in ductile iron
it is <0.01 %. Soluble oxygen content cannot be measured directly; however the activity of
oxygen can be measured with special sensors. According to Hofmann et. al [20] about 50 pct
oxygen present as SiO2, 8 ppm as FeO + MnO, the remaining being bound as silicates, mixed
oxides or more stable oxides than SiO2 such as Al2O3 or TiO2. Orths et. al [21] found by
experiment that oxygen bound as FeO + MnO varies between 25 and 50 pct of the total oxygen
content. Elbel et. al [22] also recorded the oxygen activity for FGI, CGI and SGI at 1350 oC
which are 0.97 ppm, 0.30 ppm and 0.16 ppm respectively. Mampaey et. al [23] states that
superheating and subsequent holding of a melt reduces the total oxygen content from 106 ppm
to 48 ppm. This decrease can be explained as the oxides, which present about 50 pct of the
oxygen content, goes into slag due to longer holding time. The oxygen activity is much lower
in the melt. There exist an equilibrium between dissolved oxygen and SiO2 which varies with
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temperature. Mampaey [23], reported from his experiment that oxygen activity dropped from
1.8 ppm at 1480 oC to 0.44 ppm at 1350 oC.
1.6 Introduction to current work
In this thesis we will cover all micro-structural based concepts regarding the cast iron. This
thesis contains 6 supplements. In the first two supplements, gray cast iron is researched. In the
remaining supplements graphite morphology is investigated.
1.6.1 The effect of MnS and Oxides on Graphite Morphology
At normal level of S and Mn in gray iron, MnS are formed in the melt. Oxides are formed when
inoculants are added to the melt. Many researchers have found that (Mn,X)S, where X=Al, Sr,
Ca, etc., can acts as a nucleation site for graphite [24, 25, 26, 27]. Each type of inoculant
influences the graphitizing efficiency differently [28]; for example, Sr has a higher graphitizing
efficiency than Ba and Ca. A 3D visualization was once performed of an eutectic cell and found
many small MnS inclusions within a thick graphite flake [29]. The lattice structure study of
CaS, MnS and graphite showed a close match between the lattice parameters of CaS and MnS
to that of a graphite [30]. Some authors think that Mn/S ratio influences graphite nucleation
[31]. Similarly, the content of Mn in cast iron has been investigated many times by different
researchers, whereby the ratio of Mn/S was explored with respect to the graphite precipitation
process and morphology along with its relationship to the tensile strength of cast iron [12, 32,
31, 33].
1.6.2 Austenite Growth Morphology and Latent Heat
In gray cast iron, the growth morphology of graphite and austenite are interdependent. The
nucleation of austenite has not been investigated in detail. More attention is drawn towards the
graphite nucleation and growth morphology as well as shrinkage, although mechanical
properties and shrinkage strongly depend on the austenite dendritic structure. The volume
fraction, the orientation of dendritic structure and thickness of dendrite arms has an influence
on the mechanical strength of the material. The nucleation of austenite is one of the major
disputes which is not yet solved. Liquid cast iron contains many potential nuclei while some
of them are suspected to have a role in the nucleation of the primary austenite. Si, Al, Ti and V
are suspected to be playing a role on the morphology and the nucleation of austenite [34, 35,
36]. Strong differences in shrinkage and mechanical properties can be expected between
oriented and random dendritic arrangement [35].
Alfa-quartz SiO2 has been reported to be a potential nuclei for austenite [37]. SiO2 in
combination with other type of oxides such as Al2O3, CaO, SrO, MgO and BaO reduces the
lattice dis-registry to a minimum on at least one crystallographic plane, and it will provide an
excellent nucleation site for austenite. Similarly SiC can provide a nucleation site for austenite
[38]. Pure iron power has been shown to provide a good nucleation site for austenite [39]. In
hyper eutectic alloys, graphite can nucleate primary austenite [40].
Latent heat (LH) is a property which is known now as variable [41, 42, 43, 44]. This explains
why the equilibrium diagram cannot explain the solidification process properly. A large
difference in latent heat has been observed between gray and nodular cast iron [45, 46]. A Meta
stable phase diagram can explain these differences.
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1.6.3 The Effect of Trace Element on the Transition of Graphite Growth Morphologies
To produce nodular or compacted type of cast iron, certain elements are added to the melt
which are strong de-oxidizers and de-sulfurizer, such as Ca, Ce, Mg, or La. In nodular graphite,
the attempt is always to get higher nodularity and nodule count; however due to insufficient
addition of the mentioned elements or due to other reasons, one gets other forms of graphite
particles in the microstructure which are sometime harmful for the material mechanical and
thermal properties. Chunky, compacted, vermicular and undercooled types of graphite results
in due to poor treatment of the melt. Often in heavy castings such as in wind mill or casting big
rollers, due to very long solidification times, the transition of graphite morphologies is more
prominent and larger differences are observed in the microstructure. Flake graphite can also be
result in if the sulfur content in the melt is fairly high. A variety of graphite types are observed
in cast iron, such as those shown in Fig. 2.
The transition of graphite morphology has been under debate for many decades and no one
have given any explanation that can be widely accepted. Some researchers think that only
special type of nuclei can nucleate nodular graphite but it has been observed that the same
nodular graphite can undergo transition later during its growth. There have been reported
variety type of nuclei in the nodular graphite as discussed in the previous section; however
there is evidence where nodular graphite was obtained without any inoculation. Nodular
graphite was found in a spectroscopic purity ternary alloy (Fe,C,Si) [47]. At slightly lower
purity level many curved and bent graphite crystals appeared. According to many authors, the
graphite growth morphology is related to the impurities in the Fe base liquid, [48, 49, 50, 51]
while spherodizers are not necessary to form spheroidal graphite [48, 49, 50]. External
condition can also change the graphite morphology such as in Ni-C alloy, the graphite
morphology was transformed from a rod to spheroidal shape with the application of pressure
[52]. The morphological change in the graphite is its ability to grow as a curved crystal under
certain conditions, while under other conditions, this ability does not exist [51]. It has been
observed that with a higher cooling rate, the morphology of graphite transforms from flake to
undercooled and spheroidal graphite regardless of the presence of sulfur in the liquid of grey
iron (sulfur is known to promote flake graphite).
It is commonly accepted that flake graphite iron (FGI) has a high concentration of oxygen and
sulfur, while nodular graphite iron (SGI) has a much lower oxygen and sulfur content. Various
authors have studied the effect of S and O and some metal atoms on the morphology of graphite
[48, 50, 53, 54, 29]. Atoms can be added easily in the a-direction but with a lower probability
of attaching in the c- direction normal to the monolayer [50], depending on different bonding
in the different directions. The metal atom incorporation into the graphite lattice has been
associated with the screw dislocations [54, 55, 56] and splitting and branching of the graphite,
resulting in changes in the relative orientation of the basal plane during growth [57, 58]. Wang
et al. [59] observed that fringes of graphite consist of bends in the layer. Such faults have been
observed by HRTEM analysis on a nanometre scale in spheroids [60].
1.6.4 Graphite Growth Control
Nodular cast iron has been extensively investigated during the last decades. By treating the
alloy with nodularizer, not only nodular graphite but several different types of graphite
morphologies have been observed such as vermicular, exploded, chunky, spiky, coral, and
compacted. The formation of chunky graphite (CHG) and compacted graphite is a common
16
(b)
(a) (c)
(d) (e) (f)
(g)
(h) (i)
(j) (k)
Figure 2: Different graphite morphologies in the deep etched samples. (a) compacted graphite (b) Chunky
graphite, (c) Chunky graphite/vermicular, (d) branched nodular graphite, (e) inter-dendritic chunky graphite,
(f)branched flake like graphite, (g) coarse and fine flake graphite, (h) branched coarse and fine flake graphite,
(i) rod shape and undercooled vermicular graphite, (j) flake graphite with random growth and (k) disk like
graphite.
problem in these alloys. These graphite morphologies are often found in the heavy sections.
Various reasons have been reported for the transition of graphite morphology from nodular to
other forms of graphite. One of the main reasons which comes to mind immediately is the
improper Mg treatment of the melt, or not enough treatment. Another reason could be longer
waiting times of the melt after the Mg treatment until pouring into the mould. The formation
of chunky graphite has been related to different factors such as, according to Fragues et. al [61] ,
freezing time, treatment conditions, additions of modularizers or inoculants or products bearing
Ca or Sr, this promotes the formation of CHG. According to Asenjo et al. [62], the formation
of CHG is due to mould inoculation. Nakae et al. [63] showed that larger undercooling during
the spheroidal graphite eutectic reaction produces a morphological transition from nodular to
CHG. It is not the only graphite morphology transition, there are various other transitions, such
17
as from nodular to compacted type and then towards chunky type of graphite. The reverse of
this transition is also possible and it has been observed that spherical graphite exists between
the chunky graphite cells [64]. A CHG cell was chemically analyzed for Mg, S and Sb, but
there was no significant difference in the composition of the mentioned elements in the areas
with and without CHG. However the effect of oxygen was not discussed on the graphite
morphological transition.
1.6.5 High Al cast iron
High aluminum cast iron became useful due to its oxidation resistance, high impact strength
and better wear resistance at room temperature and high temperature. This family of cast
iron Fe-C-Al is not very new. It has been researched by Löhberg et. al (1938, 1969) [65, 66],
Aleksandrov et. al [67] and Bobro [68] (1964) in Russia. Several authors [69, 36, 70, 71,
72, 73] have concluded that Al is a stronger graphitizer than Si. Aluminum segregates
negatively and reduces the solubility of C in the austenite, thus increases the graphitization.
Al stabilizes pearlite during the eutectoid reaction. Aluminum increases the eutectic
temperature by 20 oC for every percent increase in Al content in the alloy [36]. Carlberg and
Fredriksson performed unidirectional solidification experiments and found that with
increasing Al content, the solidification front progresses from smooth to an irregular front
where the two phases do not co-operate with each other, but with rising Si content the front
does not change. These authors [36] showed that the coupled zone becomes narrower for
high Al content which explains the lack of co-operation between the two phase regions.
Several authors [36, 73] have found that Al promotes coarse flake graphite in the absence of
Mg treatment. The solidification interval also increases as the Al content increases [36].
18
CHAPTER 2
MATERIALS AND EXPERIMENTAL METHODOLOGY
2.1 The effect of MnS and Oxides on Graphite Morphology

One cast iron base was used, and from this base iron, several other cast iron alloys were
prepared, while varying the S content (Table 1). Two more alloys were of different Mn content.
A high-frequency (HF) induction furnace was used to melt the alloys in a high-grade
transparent quartz tube surrounded by a graphite suscepter, under Ar atmosphere. The
maximum temperature of the melt ranged from 1300 to 1350 °C. Infrared Pyrometer was used
to monitor the temperature of the melt through the wall of the quartz tube. Commercially
available Superseed® inoculant was used in most of the experiments.
Five series of experiments were performed (see Tables 2, 3 and 4). In the first series of
experiments (ES1) inoculated melt was quenched before solidification starts, to study the type
of inclusions formed in the melt. In all other series of experiments, melt was slowly cooled
down to room temperature; however ES2 was un-inoculated and ES3 was inoculated with 0.5 %
Superseed® inoculants. One of the samples in ES4 was inoculated and the other was un-
inoculated. In the last series of experiments (ES5), samples were of variable S content and un-
inoculated. They (DSC-17 to DSC-23) were prepared under similar conditions of melting and
cooling in the differential scanning calorimeter (DSC), to analyse the precipitation of MnS in
the melt and during solidification.
Table 1. Composition of the alloys in wt.% (S = sulfur, N-Mn = no manganese, L-Mn = low manganese,
C.E = carbon equivalent (%C+(%Si/3))).
Alloy C Si Mn S Mo Cr N P Ti Cu C.E
S0.107 3.41 1.93 0.61 0.107 0.22 0.26 0.006 0.022 0.009 0.56 4.05
S0.061 3.45 1.97 0.65 0.061 0.22 0.27 0.006 0.028 0.01 0.59 4.10
S0.028 3.47 1.96 0.58 0.028 0.21 0.26 0.002 0.028 0.009 0.60 4.12
S0.021 3.44 1.93 0.64 0.021 0.22 0.26 0.003 0.026 0.009 0.59 4.08
S0.010 3.41 1.98 0.58 0.010 0.20 0.26 0.003 0.027 0.009 0.60 4.07
S0.007 3.41 1.92 0.63 0.007 0.22 0.27 0.001 0.025 0.009 0.59 4.05
L-Mn 3.22 2.37 0.04 0.013 0.13 0.28 0.016 0.002 0.005 0.69 4.01
N-Mn 3.32 2.04 0.00 0.094 0.12 0.25 0.002 0.001 0.001 0.66 4.00
Table 2. Samples quenched in brine after inoculation (except sample ES2-7). (Q= quenching,
Inoc.= Inoculation, S.Sd= Superseed®inoculant, S.C= slow cooling.)
Sample Sample Inoc. Cooling
Alloy
No. Mass (g) (wt.%) condition
ES1-1 S0.061 3.80 0.3 S.Sd Q-1170 oC
ES1-4 S0.028 4.14 0.3 S.Sd Q-1170 oC
ES1-5 S0.007 3.93 0.3 S.Sd Q-1280 oC
ES1-6 S0.061 9.11 0.5 Al Q-1250 oC
ES1-7 S0.061 15.5 0.2 Ti S.C
ES1-8 N-Mn 0.46 1.0 S.Sd Q-1300 oC
ES1-9 L-Mn 0.68 1.0 S.Sd Q-1300 oC
19
Table 3. Samples inoculated with Superseed® inoculant. The cooling rate was approximately 60
K (oC)/min for all samples.
Sample No. Sample S. Sd Inoc.
Alloy
Mass (g) (wt.%)
ES2-10a S0.107 5.25 0
ES2-10b S0.061 4.90 0
ES2-10c S0.028 5.04 0
ES2-10d S0.021 4.03 0
ES2-10e S0.010 4.05 0
ES2-10f S0.007 3.03 0
ES3-11 S0.107 5.04 0.5
ES3-12 S0.061 4.58 0.5
ES3-13 S0.028 5.04 0.5
ES3-14 S0.021 4.58 0.5
ES3-15 S0.010 4.04 0.5
ES3-16 S0.007 3.02 0.5
ES4-24 N-Mn 7.98 0
ES4-25 N-Mn 7.06 0.5
ES4-26 L-Mn 6.60 0
ES4-26 L-Mn 6.66 0.5
Table 4. Un-inoculated samples melted in a differential scanning calorimeter (DSC) at a cooling

rate of 15 K(oC)/min.
Sample No. Alloy Sample Mass (mg)
DSC-17 S0.107 128
DSC-18 S0.061 157
DSC-19 S0.028 230
DSC-20 S0.021 147
DSC-21 S0.010 167
DSC-22 S0.007 210
DSC-23 N-Mn 170
Energy dispersive X-ray analysis were performed on micro inclusions while using an EDX tool,
mounted on scanning electron microscope (SEM, S-3700N) at an acceleration voltage of 10KV
to 20 KV, depending on the size of the inclusion.
2.2 Austenite Growth Morphology and Latent Heat
Gray cast iron was investigated having the composition of alloying elements as Mn 0.6, Cr
0.27, Mo 0.2, Cu 0.6, Ni 0.03 (wt. %). Sulfur content was varied from 0.004 to 0.1 wt. % by
de-sulfurizing the alloy. The composition and experimental detail is provided in chapter 4,
Table 11. In one series of experiments, sample of variable S content were melted and cooled
down to room temperature in the DSC equipment, under similar and control conditions of
temperature. The purpose was to measure the latent heat of solidification and measure the
austenite volume fraction. Some experiments were performed by adding Al to the samples of
one composition in the differential thermal analyser (DTA) equipment and in the HF induction
furnace, to analyse the effect of Al on the austenite growth morphology and volume fraction.
The austenite growth morphology and volume fraction was evaluated by the latent heat of
solidification measured from DSC thermal analysis and from the colour etching technique.
20
2.3 Graphite Growth Morphologies
In this project, experiments were performed on pure ternary alloy of Fe-C-Si with 0.01 % S in
it. The detail of the composition, experiments list and experimental procedure is provided in
Table 5 and 6. Three types of de-oxidizers were added to the melt to study their effect on the
oxygen and sulfur content and the resulting graphite morphology. A few experiments were
performed in DSC equipment to provide a controlled environment of melting and solidification
for a better comparison to study the effect of oxygen concentration on the graphite morphology.
Another sample T640-6, which was pre-inoculated, was analysed under SEM, after performing
ion etching on it. Other samples which were treated with de-oxidizers, were also cross section
polished with iron and ion etching was performed on them, to study the graphite growth
morphology under field emission (FE) SEM.
Table 5. Experiments and experimental conditions.
Table 6. Investigated alloys composition.
2.4 Effect of trace elements on the transition of graphite growth morphology

The purpose of the project was to investigate the effect of trace elements individually on the
graphite growth morphology, therefore a pure base material was required to do experiments
with it. Three alloys were prepared for this purpose, the first alloy A1 was a ternary alloy of
hyper eutectic composition, having 0.01 % S as well (Table 7). The second and third alloy A2
and A3 was prepared by alloying ultra-high pure Fe and C to make a binary alloy of hypo and
hyper eutectic compositions, respectively.
Experiments were performed in DSC, DTA and HF induction furnace. The maximum
temperature of the sample in the DTA and DSC furnaces was set to 1450 °C and 1400 °C,
respectively. A cooling rate of 10 °C/min was used in both cases. The maximum temperature
of the samples melted in the HF furnace was between 1450 and 1500 °C, and the cooling rate
was approximately 50 °C/min in all the samples. Different type of additives (S, O, N, P, Se, B
and F) were added to the melt prepared from A1, A2 and A3 alloy, in the HF induction furnace,
under high purity argon atmosphere. The additives were added in the form of compound with
iron. The detail of the alloy composition, additive type, amount, and experimental conditions,
are provided in Table 1 and 2, in the supplement 4. Three more samples were prepared without
any addition, to compare them to the samples which were treated with various type of additives.
Some experiments were performed in DSC on the ultra-pure binary alloy, by adding S and O
21
to them and analysing the latent heat of solidification. Metallographic analysis was performed
on perpendicular sections of all the samples. Some samples were deep etched with 5 % brome
methanol solution at room temperature. Samples were extracted from flake, nodular and
undercooled graphite with the help of focused ion beam (FIB) technique, for transmission
electron microscope (TEM) and high resolution TEM examinations.
Table 7: Compositions of the investigated alloys (Fe-balance).

Alloys C Si S C.E
A1 3.84 2.12 0.01 4.54
A2 3.5 0 0 3.50
A3 > 4.7 0 0 > 4.7
2.5 Graphite growth control
A low Mo content alloy was prepared in a vacuum furnace and cast into rod shape, in Cu block.
The composition of the alloy after FSM treatment and inoculation included the following:
(wt. %) 3.68 C, 2.22 Si, 0.015 P, 0.135 Mo, 0.005 S, and <0.09 Mg balanced with Fe. The
detail of additives, and list of experiments is provided in Table 8 and 9.
Experiments were performed on the alloy by adding 4 type of inoculants and one type of
FeSiMg alloy. The intension of the experiments was to analyse the effect of inoculation
sequence, inoculation temperature and type of inoculant. All the experiments were performed
under argon atmosphere in an alumina crucible. HF induction furnace was used to melt the
alloy in the presence of a graphite suscepter. Temperature was monitored and recorded by using
S-type thermocouple. Thermal analysis was performed on the data obtained from the
temperature data logger.
Table 8. Composition of the inoculants used in the experiments
Table 9. Experimental conditions for both of the alloys. In each experiment, 2 % FSM
and 0.7 % inoculant were added.
Exp # Inoc. % & type Inoc. sequence Inoc. T ( oC )
S1 0.7 % SCA 1st inoc 1420
S2 0.7 % SCA 1st FSM 1420
S3 0.7 % SCA Combine 1460
S4 0.7 % CCA2 Combine 1390
S5 0.7 % CCA2 Combine 1350
S6 0.7 % CCA1 1st inoc 1420
S7 0.7 % CCA2 1st inoc 1420
S8 0.7 % CA 1st inoc 1420
22
2.6 High Al cast iron
Alloys were prepared at the laboratory by using a HF induction furnace. Fourteen experiments
were performed, under argon atmosphere. The details of the experiments is provided in Table
10. FeSiMg (FSM) was added to the melt for Mg treatment. The composition of FSM was: 5 %
Mg, 0.3 to 0.7 % Ca, 47 % Si and balance Fe. Commercially available inoculants which we
named as CCA1 (0.75-1.25 % Al, 0.75-1.25 % Ca, 1.5-2 % Ce, 70-76 % Si and Fe balance)
and CCA2 (same composition as CCA1 but CCA2 surface is coated with about <1 %
O/S ),were used for inoculation.
In the first 2 experiments, Al was added during the alloy preparation in a vacuum induction
furnace. The samples microstructure was examined without Mg treatment and inoculation.
Samples 3 to 8 were prepared by adding and Si prior to Mg treatment. The effect of variable
Al and Si content on the graphite morphology was investigated in these samples. From 9 to 12,
samples were treated with FSM and de-oxidizers and with inoculant. These experiments were
performed in order to control the graphite morphology. The last two experiments were
performed without Mg treatment, but they were inoculated with CCA 1. The microstructure of
a few samples was colour etched with Klemm I, to analyse the segregation of Al and Si.
Table 10. Experiments and composition of the samples. (C.E= %C + %Si/3 + 0.125 % Al)
23
CHAPTER 3
RESULTS
The results of all the projects are combined in this chapter, in separate sections. The detail of
the results will not be shown here, only the important results will be presented. There might be
some results which are not included in the scientific articles due to page limitations, will be
presented in this chapter.
3.1. The effect of MnS and oxides on graphite morphology

3.1.1. EDX analysis
By using EDX micro-analysis tool, small inclusions on the sample surface, either quenched or
slowly cooled, were analysed. From the quenched samples, analysis showed many different
type of oxides such as Al2O3, SrO, CaO/S and SiO2 were found in the centre of MnS particles
(Fig. 2). Mo was also found together with Mn to form a complex of (Mn, Mo)S. Graphite was
then precipitated around the MnS particles. With decreasing S content, the size of MnS
particles was decreasing. Also AlN and TiN particles were found but they did not play any role
in the graphite nucleation, but rather they were found to promote carbides.
By slow cooling of the samples, various type of particles were found. Mo was found to form a
complex compound with Cr as (Mo,Cr)S in the absence of Mn, often attached to a graphite
flake. Mo2C phase was found attached to graphite, in the samples with and without Mn.
3.1.2. Effect of sulfur content and inoculation on MnS growth morphology
MnS grew in a variety of shapes. In un-inoculated samples with higher sulfur content, large
size MnS inclusions of variety of shapes were found, connected with graphite flakes (Fig.
3(a,b,c,d)). A significant modification in the growth morphology of MnS was observed at lower
MnS particle sizes (Fig. 3(e, to i)). In this case, MnS grew as a faceted cubic structure on
complex oxides. Straight, thick and long graphite flakes (compared to un-inoculated samples)
were nucleated on the MnS particle (Fig. 2(e to i)). Other shapes of MnS, such as the hexagonal,
triangular or trapezoidal forms, occurred as a result of the different cutting planes associated
with MnS particles, hereby referred to as regular MnS particles (while all other shapes would
be categorized as irregular MnS particles). A statistical analysis was performed on the un-
inoculated samples and inoculated samples (Suppl. 1: Table III). A significant difference was
observed in the shape of MnS particles depending on whether the samples were inoculated or
un-inoculated. Above a certain limit of sulfur (e.g 0.021wt. %), MnS particles were regular but
by increasing the sulfur content, MnS particles growth becomes unstable and irregular shape
particles were obtained. MnS nucleation on Oxides or sulfides (Al2O3, SiO2, SrO, CaO, and
CaS) brings stability in growth to MnS and modifies growth morphology from an irregular to
a regular faceted cubic structure, even at a higher sulfur concentration (Fig. 4). Due to more
number of nucleation sites for MnS nucleation, the size of MnS will decrease accordingly as
shown in Fig. 4. In the absence of oxides in the melt, MnS grew with an irregular geometry
consisting of small and large sizes according to the amount of sulfur present in the alloys
24
(Figure 3(a, b, c, d)). Below sulfur content of 0.028 wt. %, all MnS particles were regular in
shape (Fig. 4).
Figure 3. EDX analysis of various types of inclusions in the quenched and slow cooled samples.
Inoculated samples demonstrated a significant reduction in the size of MnS inclusions,

particularly in the alloys containing high sulfur content (Suppl. 1: Table V, ES3-11 (S
0.107%) and ES3-12 (S 0.061)) when inoculated, resulted in 50% and 39% respectively
increase in small size (0.5 to 2 μm) of MnS particles.
25
Figure 4. Growth morphologies of MnS. (a,b,c,d) Un-inoculated sample ES-10a. (e,f,g,h,i) Inoculated samples ES3-
11 and ES3-12.
Figure 5. Statistical analysis of size distribution and percent regular shapes of MnS in inoculated and un-
inoculated samples at different sulfur concentrations in the base alloys.
3.1.3. Effect of sulfur content and inoculationo on the graphite growth morphology
This section addresses the results of un-inoculated, inoculated and DSC experiments. The
microstructure showed a large difference in the graphite morphology while changing the sulfur
concentration from high to low level for the same composition of the alloys.
26
Figure 6. SEM (BSE) images showing different graphite growth morphologies at four different sulfur
concentrations (S= 0.107, 0.061, 0.028, 0.01 wt. %) and treatments. (a,b,c,d and i,j,k,l) Un-inoculated, (e,f,g,h)
0.5 wt. % inoculated. Each column of images show same sulfur concentration in the samples.
Figure 7. Graphite growth morphologies in the absence of Mn in the alloy. Slow cooling of the alloys N-Mn and
L-Mn. (a) N-Mn alloys, un-inoculated. (b) N-Mn alloy, 0.5 wt. % inoculated (c) L-Mn alloy, un-inoculated, and
(d) L-Mn alloy, 0.5 wt. % inoculated.
27
In the un-inoculated samples, the graphite morphology appeared to change from type-A
graphite flakes to an inter-dendritic flake graphite (coarse type, oriented between the dendrites)
and undercooled fine graphite (ultra-fine flake graphite, interconnected with each other)
structure between the dendrites, as shown in Fig. 6(a, b, c and d). Inoculants significantly
modify the graphite structure by causing the growth of a randomly oriented type-A graphite
structure (Fig. 6(e, f and g)). In the samples with a sulfur content of less than 0.01%, the
inoculants could not avoid forming fine undercooled fine graphite structure (Fig. 6(h)). After a
deep etching of the sample with a sulfur content of 0.01%, the undercooled region of fine
graphite had an interconnected network with fine graphite flakes (Fig. 6(l)). Those samples
having high sulfur content (0.107 wt. %) were melted and cooled slowly to room temperature
in the DSC showed inter-dendritic and oriented graphite structures (Figure 5(i)). For the sample
S=0.028 %, the graphite structure was partly inter-dendritic with a small fraction of
undercooled fine graphite structure. Samples with sulfur levels less than 0.028 exhibited
completely undercooled fine graphite structures (Figure 6(k, l)). After a careful analysis of the
sample with S=0.021 %, a few small-sized (≤1μm) MnS particles were observed at the
periphery of austenite dendrites, but the MnS particles could hardly be observed in the sample
with S=0.01 %, as the sulfur content was much lower while keeping in mind the non-
equilibrium solidification which may not match the theoretical predictions (Fig. 5(l)).
In those alloys where there was no Mn but normal sulfur level and a small amount of Mo,
resulted in curved and branched flake graphite. Precipitates of (Mo, Cr)S and Mo2C were found
in connection to graphite flakes (Fig. 7). The eutectic undercooled fine graphite were heavily
branched and entangled in the samples having Mo and no Mn. However inoculation modified
the graphite morphology to less entanglement and the graphite morphology was approaching
to a type A like structure.
28
3.2. Austenite growth morphology and latent heat
The sulfur concentrations in the alloy have shown an influence on the austenite growth
morphology. In Fig. 8, four samples of different sulfur concentrations melted and solidified in
DSC. The graphite structure was similar in samples S0.061 and S0.028 (Fig. 8(b,c)), where the
austenite dendritic structure did not show any significant difference. Below a sulfur content of
0.028%, the microstructures showed ultra-fine eutectic graphite flakes (Fig. 8). In the last
sample S0.004 (Fig. 8(d)), one can notice a significant change in the austenite dendritic
structure compared to the other samples. The graphite structure consisted of inter-dendritic
ultra-fine flakes.
Figure 8. Colour etching of DSC samples, prepared with cooling rate of 10 oC/min. a S= 0.061 wt. %, (C 3.45,
Si 1.98), b S= 0.028 wt. %, (C 3.47, Si 1.97), c S= 0.013 wt. %, (C 3.48, Si 1.917), d S= 0.004 wt. %, (C 3.34, Si
1.94), c S= 0.013 wt. %, (C 3.48, Si 1.917), d S= 0.004 wt. %, (C 3.34, Si 1.94).
The effect of Al was investigated by adding a small amount of aluminum (0.025% and 0.05 %)
to the samples in DTA prior to melting. However the higher addition, 0.05% Al caused
thickening of the dendritic structure (Fig. 10). At a relatively faster cooling rate (57 oC/min, in
the HF furnace), fine austenite dendrites grew along one direction with large eutectic colonies
(Fig. 10(a)). By inoculation of the same alloy with 0.025% Al (after melting in the HF furnace),
randomly oriented austenite dendrites were observed, together with large number of the
eutectic colonies (Fig. 10(b)), compared to the un-inoculated sample (Fig. 10(a)).
The volume fraction of austenite was calculated as 0.19, 0.20 and 0.25 on samples, un-
inoculated, 0.025% Al and 0.05% Al inoculated, respectively. The standard deviated in the
values were 0.006, 0.003 and 0.007 respectively. Above a certain limit of Al addition, the
austenite volume fraction increases. The dendritic structure was denser in the samples
inoculated with 0.5% Al, compared to other samples, as shown in Figures 10 and 11. The
observations made on the austenite dendrites orientation and structure is qualitative due to the
difficulty of correctly marking the dendrites in Figure 10, but the average values of secondary
dendrite arm space is decreasing with increasing addition of aluminum (from Figure 4), with
the values from 47 μm (0.00 % Al) to 45 μm (0.025 % Al) and then 35 μm (0.050 % Al).
29
By increasing the aluminum content to 0.05%, the austenite dendrites were thicker and random,
while the eutectic colonies appeared as agglomerated and constructed a large network (Figure
10(c)). A clear difference can be observed in the graphite structure between the un-inoculated
and inoculated with different amount of Al as shown in Fig. 12, however the volume fraction
of graphite (from Fig. 12) was 13, 11, 13 for 0.00 % Al, 0.025 % Al and 0.050 % Al inoculated,
respectively. The volume fraction was measured in a similar way as that for austenite volume
fraction, from an analysis area of 5.26 mm2 of a single image taken at 50x using SEM.
Figure 9. SEM (SE) micrographs of the DSC samples (10 oC/min) having variable sulfur content. (a). S=
0.107 wt.%, (b). S= 0.061 wt. %, (c). S= 0.028 wt. %, (d). S= 0.021 wt. %, (e). S= 0.007 wt. %.
30
Figure 10. Colour etching of DTA samples, prepared with cooling rate of 10 oC/min. a- No inoculation, b- Al=
0.025 wt. %, c- Al= 0.05 wt. %.
Figure 11. Colour etching of samples prepared in H.F induction furnace (using graphite suscepter), with
cooling rate of approximately 57 oC/min. a No inoculation, b Al= 0.025 wt. %, c Al= 0.05 wt. %.
Figure 12. SEM (SE) images of the samples prepared in H. F induction furnace (using graphite suscepter),
with cooling rate of approximately 57 oC/min. a No inoculation, b Al= 0.025 wt. %, c Al= 0.05 wt. %.
31
3.3. Graphite growth morphologies
3.3.1. De-oxidation of the melt using pure Mg.
Mg treatment resulted in different types of graphite morphologies. There were areas where the
nodularity was high and in areas of the sample, the nodularity was low and flake, vermicular
type of graphite was present. There were many MgO particles in microstructure which were of
large and small sizes. In some cases MgO particles were attached to a graphite flake but in
another example MgO was found in the centre of a graphite nodule. Also there are many small
sized (about 1 micro) MgS particles in the matrix which were not attached to any graphite. In
the Fig. 13, an eutectic cell is shown which have round graphite particles at the outer boundary,
as shown with an arrow. Also there were large amount of nano sized MgO particles in the
matrix (Fig. 13).
MgO and MgS particles
All MgO particles.

MgO
MgS
MgO MgS
MgS
Figure 13. Pure Mg treated sample. All encircled particles are MgO.
32
Ion etching of the Mg treated sample revealed the growth morphology of the graphite nodules
and compacted type of graphite. It is evident from these images that the graphite growth is
along circumference in the nodular graphite as shown in Fig. 14. The undercooled flake
graphite have growth along the length of the graphite. In compacted graphite, there exist
straight flakes locally of shorter lengths, but overall the growth in random and grow in different
directions. In other words, the flake like growth is interrupted at short intervals and the growth
directions is being changed, in compacted graphite (Fig. 14).
Figure 14. Ion etching of the Mg treated sample, shows the growth morphologies of nodular graphite and
compacted type of graphite.
3.3.2. De-oxidation of the melt using pure Ca.

The microstructure showed large number of perfectly round nodules of various sizes and some
other forms of compacted graphite which were mostly precipitated inside the shrinkage pores
(Suppl. 3: Fig. 4d), with a complete absence of undercooled fine graphite (Fig. 15). The fraction
of graphite in this sample was less due to the formation of CaC2 (because of unusually high
addition of Ca) which can stabilizes or nucleate cementite. Due to multiple nuclei of CaO/S
and agglomeration, a compacted like graphite was produced as indicated with arrows in Fig.
15, but in fact they are nodules connected to each other in line. The middle area of the nodule
as shown in the encircled image in Fig. 15, probably shows carbon or graphite with high amount
of defects.
The Ca treated sample when re-melted, with low oxygen content resulted in fine undercooled
graphite together with some coarse graphite flakes (Fig.16), but with high oxygen content, the
33
Graphite in shrinkage pore Graphite in shrinkage pore
Figure 15. Ion etching of the Ca treated sample, shows nodular graphite, compacted type of graphite and graphite
precipitated in the shrinkage pores.
No addition 1 wt. % FeO addition
Figure 16. Re-melting of Ca treated sample in DSC, with and without oxygen
addition.
34
microstructure consisted of extremely fine vermicular type of graphite, with no trace of coarse
flakes (Fig. 16).
3.3.3. De-oxidation of the melt using pure Sr
The sample treated with pure Sr contained mostly flake graphite; however a small area (about
5%) at the top edge of the sample surface, contained large size irregular graphite particles of
various sizes as shown in Fig. 17. After ion etching, there were some particles which probably
contained carbon as indicated encircled in Fig. 17, also the inner part of the nodular graphite
in Fig. 17, seems amorphous. The growth mechanism in the other large size irregular graphite
was flake-like, but with many different orientations. The flake graphite consisted of layers of
graphene connected to each other. The ions bombardment have caused distance between the
layers, at the surface.
Figure 17. Sr Treated sample, ion etched sample.
3.3.4. Star like growth mechanism in the nodular graphite

A sample (T640) which was pre-inoculated and Mg treated (provided by Jaques Lacaze,
CIRIMAT, ENSIACET, Université de Toulouse, France), was etched with ions perpendicular
to the surface. A star-like growth of the graphite was observed in the centre of the graphite
nodules (Fig.18). The branches were extended outward to some distance from where onward
the circumferential growth mechanism was dominant. Those nodules with star-like growth,
35
emerging from the middle of the graphite, do not seem to have any inclusion in the middle.
The nodules with an inclusion (nuclei) in the centre had circumferential growth by following
the shape profile of the inclusion. In Fig. 18, the central part (encircled) did not have any
inclusion, but the graphite formed in layers. There should be no effect of the argon ions on the
surface of graphite due to the usage of low voltage and for short time interval.
Figure 18. T640 sample, quenched at eutectic temperature. InLense detector images after Ar ion etching using
PEC’S.
36
3.4. The effect of trace elements on the transition of graphite growth morphologies
3.4.1. Effect of S, F, O, P, N, B and Se on graphite morphology
Ultra-pure binary hypo eutectic alloy A2 resulted in compacted and vermicular type of graphite
morphology, without any addition (Fig. 19, A2). Alloy A3, which was hyper eutectic binary
ultra-pure alloy, gave us a mixed type of graphite morphologies which includes flake type,
compacted type, nodular type, rod like and vermicular graphite (Fig. 19, A3). In both samples
A2 and A3, three types of rod graphite could be observed: one type with an even surface, a
second type with a more un-even surface and a third with a cone-headed growth mechanism.
The effects of S, F, O, P, N, B and Se on the graphite morphology are described below.
Effect of Sulfur: The effect of sulfur is illustrated by comparing sample A2 in Fig. 19 with
samples A2-S in Fig. 20. By increasing the sulfur content, the flakes became increasingly thick,
long and bent, as observed in Fig. 20(A2-S).
Effect of Oxygen: The effect of oxygen on the graphite morphology is illustrated by comparing
samples A2 and A2-O. An increase in oxygen considerably decreased the fraction of long rod
type graphite, and the vermicular and spherical type of graphite and fine rod type undercooled
graphite were favored (Fig. 20(A2-O)).
Effect of Fluorine: In the fluorinated sample (A2-F), the graphite morphology was slightly
modified compared with sample A2; however, more vermicular graphite was observed (Fig.
20(A2-F)).
Effect of Phosphorous: As observed in the fine eutectic graphite area in Fig. 20 (A1-P), flakes
of graphite are formed and precipitates of Fe3P and Fe3C are observed close to the graphite
flakes.
Effect of Nitrogen: By comparing sample A2 with A2-N and sample A3 with A3-N (Fig. 19,
20), the N-treated samples contained more rounded graphite particles (Fig 20(A2-N, A3-N))
and more rod type graphite than the untreated ones (Fig. 19(A2, A3)).
Effect of Boron: The primary graphite was precipitated in long, curved and branched flakes,
homogeneously distributed in the matrix (Fig. 20(A3-B)). The eutectic graphite was more
branched and grew out from the primary flakes of graphite.
Effect of Selenium: The addition of selenium resulted in flake graphite; however, the primary
flakes were longer, with small branches formed during the eutectic reaction, as observed in Fig.
20(A3-Se).
3.4.2. HRTEM study of spheroidal, flake and fine undercooled graphite
The high resolution TEM study showed the graphite inter-lamella spacing is different in
different type of graphite morphologies, compared to the known distance between. The spacing
between the lamella was the largest in nodular graphite and in the undercooled fine graphite, it
was slightly larger, but in flake graphite, the distance between the lamella was close to the
value known for pure graphite. By analyzing the HRTEM images, we found many defects in
basal planes such as bends and vacancies (Suppl. 4: Fig. 3 to 7).
37
3.4.3. Latent heat measurement
The latent heat was analyzed during cooling of the samples and was observed to be reduced by
approximately 39 % in the oxygen-treated samples compared with the un-treated sample (Suppl.
4: Fig. 8). This result indicates that the graphite in the sample containing oxygen evolved less
energy due to the formation of vermicular or undercooled graphite, while the graphite in the
untreated sample and the S-treated sample released higher energy.
A2 A2 A2
A3
A3
A3
A3
Figure 19. SEM images of the samples from alloy A2 and A3, with no addition.
38
A3-N
Figure 20. SEM images of the samples from alloy A1, A2 and A3, with addition of S, O, F, N, B and Se.
39
3.5. Graphite growth control in nodular cast iron
The microstructural results show a variety of graphite morphologies. There were different
factors which affected the graphite morphology such as inoculation sequence, inoculation
temperature and type of inoculant. By adding FSM prior to inoculants resulted in less
nodularity and nodule count but when the same type of inoculants were added prior to FSM,
the graphite morphology was modified and higher nodularity was obtained. Inoculants
temperature, on the other hand, have an effect on the vaporization of Mg. The higher is the
temperature, the high would be the loss in Mg, but at lower temperature (practically possible
values), maximum nodularity was obtained (Fig. 22).
Figure 21. SEM images of samples. (S1) Inoculation first and FSM addition latter, (S2) FSM addition first and
inoculation later, ((S3) treatment at 1460 oC, (S4) treatment at 1390 oC, (S5) treatment at 1350 oC.
40
By carefully analyzing the microstructure of various samples, it was evident that the transition
from one form to another form occurs at different solid fraction (Fig. 21). In some cases the
transition occurred from nodular to non-nodular graphite at the beginning of solidification but
due to the formation of MgO close to the end of solidification, again the transition from non-
nodular to nodular graphite occurred which is also shown in the color etched images (Fig. 21).
But in some cases, vermicular graphite were found at the end of solidification.
Figure 22. Statistical analysis of the graphite particles in the samples
41
3.6. High Al cast iron
High Al cast iron was found to have flake graphite morphology, even though the sulfur content
was quite low in this alloy. By adding sulfur to the alloy, the flake graphite became thicker and
longer (Fig. 23). By adding Mg to the alloy, nodules were obtained but overall the sample
contained low nodularity. There were many chunky graphite and vermicular type of graphite
in the sample. Different additives and procedures were tested on the alloy to increase the
nodularity but it was difficult. Even higher amount of FeSiMg did not work effectively. The
addition of pure Ca and Sr was not easy due to their highly volatile nature. By adding inoculants,
which contains Ca and Ce in large amount, in the absence of Mg, relatively higher nodularity
was obtained.
With increasing Al content in the alloy, the fraction of fine vermicular graphite and chunky
graphite increased. Due to higher amount of Al and Si, it was difficult to produce high
nodularity in this alloy.
Figure 23. SEM images of the sample. (SiAl-1) No addition, (SiAl-2) 0.05 % S addition, (SiAl-10) 0.5 % Mg,
0.5 % Ca, and 2 % FSM, (SiAl-13) 3 % CCA1 and 0.2 % Ca, (SiAl-14) 5 % CCA1 addition.
42
CHAPTER 4
4. DISCUSSION
4.1. Relationship between inoculants and MnS in gray cast iron

Inoculants are added to the melt at a high superheat and they dissolve quickly after the addition.
Experiments showed that the formation of oxides/sulfides at a certain temperature in the melt
or during the solidification depends on the concentration of the deoxidizers (Al, Sr, Ca, etc.)
and sulfide forming elements (Ca, Mo, Mn, etc.). The nucleation of any oxide/sulfide particle
at different superheats or during the solidification process could change the growth morphology
of the complex oxide-sulfide particle that can affect as well the nucleation of graphite in
different ways. The sequence of nucleation of oxides/sulfides is important to understand
because this helps in finding out the appropriate concentration limit of an inoculant. The
possibility of nucleating an oxide/sulfide particle in the melt is analysed by using the
thermodynamics of the inoculants. Detailed formulation and assumptions are available in
Supplement 1.
Figure 24. Equilibrium and supersaturation of MnS and Mo2S with S at three different temperatures.
The oxygen concentration in the melt is available in two forms: oxygen dissolved in the Fe
melt and oxygen present in a combined state as FeO or SiO2. Each element of an inoculant has
a different affinity towards oxygen, which causes the nucleation of those oxides at a certain
oxygen concentration in the melt. The solubility of oxygen decreases in the melt with
decreasing temperature. It was assumed that the dissolved oxygen in the melt remains in
equilibrium with the dissolved Si in the iron, which also implies equilibrium between Si and
SiO2. From experiments it was observed that MnS was nucleated upon oxides which was
43
attached to a graphite flake. Experiments also showed that oxides modifies the MnS particle
geometry and size. Therefore it is important to nucleate oxides first in the melt and then MnS
could be nucleate upon them. The possibility of nucleating MnS at different temperatures is
discussed in Fig. 24.
The nucleation of MnS at any temperature depends on the solubility product of Mn and S, not
only on one of them either Mn or S. If there is high Mn in the melt and low S in the melt or if
there is low Mn and high S in the melt but the solubility product gives the same value then they
would nucleate at the same temperature.
The concept of sequential nucleation was introduced. The best result we could expect would
be if oxides are nucleated before the solidification starts and MnS gets nucleated just after the
oxides are formed. The nucleation of oxides is analyzed in Fig. 25, which shows that SrO will
nucleate prior to Al2O3. In this situation oxides will provide nucleation sites for MnS
precipitation. The thermodynamics calculations performed in Fig. 24 shows that MnS could be
precipitated just prior to solidification when the S and Mn content is 0.029 and 0.6 %
respectively. Similarly during solidification, due to enrichment of the inoculants, Mn, S, and O
in the melt, it is possible to form new oxides and sulfides, but again it would be preferable to
nucleate oxides prior to MnS nucleation (Fig. 25). Certain oxides such as SrO could be
nucleated prior to MnS and it can provide nucleation sites for MnS (Fig. 27).
Figure 25. Equilibrium and supersaturation analysis of SrO, Al 2O3 in the melt, prior to solidification, at
variable temperatures.
Since it was observed that graphite was nucleated upon MnS, hence one should increase the
number of MnS particles in the melt, so that during solidification, there should be large amount
of MnS/oxide particles available, which could provide nucleation sites for the graphite flakes.
This would help in providing flake and random graphite structure which will have large
influence on the properties of the material. In order to fulfil this condition, one should control
44
the composition of Mn and S in such a way that MnS gets nucleated homogeneously just before
the solidification starts.
Figure 26. Homogeneous nucleation of MnS during solidification.
Figure 27. Homogeneous nucleation of SrO during solidification.
45
4.2. Effect of S and Al on the austenite growth morphology and latent heat
measurement
The volume fraction of austenite was calculated by using color etching technique. It was found
that the volume fraction of austenite was increasing with increase in the Al content and the
dendritic structure was becoming denser as well. The average secondary arm spacing in the
dendrites was decreasing with increasing Al content. The austenite volume fraction was
changing with the sulfur concentration in the melt. The austenite volume fraction calculated by
DSC can be trusted more than the microstructure, since it gives a volume information. The
closest value to that of DSC is the one obtained from the microstructure using color etching
technique. Lever rule and ThermoCalc both have underestimated the austenite volume fraction
(Suppl. 2: Table 1).
Graphite morphology has strong dependence on the austenite growth morphology and austenite
volume fraction. The early formation of graphite flake after the solidification has been started,
would reduce the carbon content in the melt which gives a driving force for the austenite
nucleation and results in high rate of formation of austenite (Fig. 28c). From our previous
research it was verified that S content in the melt have strong dependence on the flake graphite
growth morphology. This gives an indication that, samples having high sulfur concentration
would affect the rate of formation of austenite and volume fraction of austenite as well (Table
1).
At the early stages of growth, the austenite dendrite can be considered as a sphere. Assuming
that N number of austenite dendrites are nucleated by N number of nucleation sites. The total
heat flow transported away from the melt is the sum of the cooling heat flow from the melt and
solidification heat from freely floating crystals. The solidification heat (of crystals nucleated)
as a function of time taking into account and growth rate of freely floating crystals is given by
eq. 1 [74].
𝑑𝑄 𝑑𝑅
= 4𝜋𝑅 2 ( ) 𝑓𝑁𝜌(−𝛥𝐻). . … … … … … . .1
𝑑𝑡 𝑑𝑡
Where “dR/dt” is the growth rate of the dendrite at the initial stage, “f” is the fraction solidified
inside the nucleated crystal, “N” is the number of nucleated crystals, “ρ” is density, “-ΔH” is
the heat of fusion and “dQ/dt” is the heat of solidification of the nucleated crystals of austenite
dendrites. It is obvious from the equation that the growth rate of the dendrites reduces with
increasing number of nucleated austenite crystals and vice versa. But in practice the latent heat
(LH) of austenite changes for alloys of different sulfur contents (Table 11). The eutectic latent
heat depends on the graphite growth morphology. In the sample having high sulfur content,
have normal flake structure and the eutectic latent heat is also high for those samples. The total
heat of solidification is also high for the sample having high sulfur content, except sample S
0.004, due to low CE.
46
Table 11. DSC thermal analysis on samples of different sulfur compositions. The alloying dements in the alloys were 0.6 %Mn, 0.27 % Cr, 0.22 % Mo,
0.03 % Ni and 0.6 % Cu.(P.D phase diagram, c austenite, q density)
47
(a)
(b)
(c)
Figure 28. Heat of solidification plotted versus temperature for all samples, obtained by using DSC. (a) Samples
S = 0.061 and 0.028. The shaded area shows the energy of the respective transitions. (b) Samples S = 0.107, and
0.021, (c) Rate of formation of austenite versus T
48
4.3. Graphite Growth Morphologies
In the cast iron melt there is S and O, among the other trace elements which are the most
important ones and have been investigated extensively. In this research, the effect of strong de-
oxidizers and de-sulfurizer was experimentally investigated. It was found that Mg alone can
work as de-oxidizer and de-sulfurizer and produce nodular graphite; however the efficiency of
Mg is less due to the presence of large number of compacted and undercooled flake graphite
in the sample. By closely analysing the microstructure, it was found that there are many MgO
and MgS particles inside the nodule and outside the nodules (in the matrix) as well. This gives
an indication that not every MgO is nucleating graphite nodule and also it is not important that
a MgO particle would nucleate a nodular graphite. It is shown in the results that MgO and MgS
paticles are attached to flake graphite. These observations have shown that, the nucleation of
different forms of graphite does not depends on the type of nuclei but it depends on the
composition of liquid in term of trace elements which controls the graphite growth morphology.
To support this statement, further experiments were performed using pure Ca and Sr.
Ca treatment gave nodular graphite. While not taking into account the shrinkages and the
graphite precipitated into those shrinkages, one can easily reach to a conclusion that due to
effective removal of O and S from the melt by Ca (being a strongest de-oxidizer and de-
sulfurizer, Fig. 29), the graphite morphology was nodular. By re-melting the Ca treated samples,
due to the absorption of oxygen into the melt from the surrounding and surface of the sample,
once again the graphite morphology was undercooled flake like and vermicular like. By adding
oxygen into the melt intentionally, in another re-melted Ca treated sample, extremely fine
undercooled vermicular type of graphite was formed which is typically due to high oxygen
content. Another verification of our hypotheses can be found when we treated the melt with
pure Sr which is a strong de-oxidizer but a week de-sulfurizer. We obtained mostly flake
graphite but a small fraction of compacted and nodular graphite was also formed in one corner
of the sample which was due to the Sr rich region. Sr being a week de-sulfurizer and strong de-
oxidizer, removed oxygen from the melt but S level did not changed over all, which produced
flake graphite. This observation showed that, the type of nuclei is not controlling the
morphology of graphite, but it is rather the composition of the melt which gives a defined
morphology to the growth of a graphite particle. For instant sample with higher S content but
very low oxygen content would result in normal fine flake graphite (such as in the Sr treated
sample) but a sample having very low sulfur and low oxygen content would resulted in nodular
graphite (such as the Ca treated sample).
From the ion etching of the graphite, it was interesting to found that the growth mechanism of
a nodular graphite was circumferential in our alloys. In another sample which contains
relatively high Si content, there was star like growth morphology of the graphite at the
beginning and later the morphology was transformed towards circumferential growth
mechanism. The branches emerging from the centre of the nodules in the star like growth of
graphite, appears like dendritic growth mechanism of graphite. The reason behind this growth
mechanism is not investigated in detail, however we can speculate that this type of growth
mechanism is due to the lattice structure defect in the graphite at the beginning of growth. The
hexagonal lattice structure might have been distorted and due to high silicon content, a mix of
diamond cubic and hexagonal lattice structure might have been formed which have given a
dendrite like growth mechanism to the graphite. During solidification, the silicon content
would reduce in the melt, then the hexagonal lattice structure might have been become
49
dominant, resulting in the normal circumferential growth mechanism of graphite. The other
possibility of such a growth mechanism would be the presence of nano sized C-C or C-Si and
even C-Fe clusters in the melt which changes the kinetics of the graphite growth.
Figure 29. Ellingham updated diagram [76], thermodynamic energy of formation of different oxides and
sulfides.
50
4.4. Relationship between the trace elements and graphite growth morphologies
Cast iron is highly impure alloy. Beside many alloying elements, there can be various type of
trace elements in the melt of cast iron. Among those, certain type of trace elements have
influenced the graphite morphology. In our research we focused on O, F, S, N, P, B and Se.
The experimental results on mentioned trace elements have shown different results for different
trace elements. The effect of these traces can be divided into mainly three parts, flake stabilizer,
vermicular/compacted type stabilizer and neutral. S, Se and B were all found to stabilize flake
morphology. O and F (halides) were stabilizing vermicular or compacted type of graphite
growth morphology. N was found to have least effect on the graphite growth morphology,
however P was stabilizing flake morphology but not as effective as S does.
The theatrical analysis on the above mentioned trace elements gave satisfying results. We
believed that the transition in the graphite growth morphology was at the atomic scale and these
elements were playing a role in altering the growth mechanism of the graphene. Avogadro
software was chosen to simulate the effect of trace elements on a small graphite layer which
has few atoms inside. It is designed for cross-platform use in computational chemistry,
molecular modelling, bioinformatics, materials science, and other related areas. It is an
advanced molecule editor and visualizer. It is a powerful tool for analysing simple organic and
other molecules while applying different kind of force fields. There are 5 types of force fields
for different applications but what we used was chemical force field which is basically for
simple organic molecules. The structure is optimized by Avogadro software while using
chemical forces to minimize the energy by considering all types of energies in the structure
expressed by the equation 𝐸𝑡𝑜𝑡 = 𝐸𝑏 + 𝐸𝑎 + 𝐸𝑡 + 𝐸𝑣𝑑𝑤 + 𝐸𝑒𝑙 , where Eb is the bond stretching
energy, Ea is the angle bending energy, Et is the torsional energy, Evdw is the van der Waals
energy and Eel is the electrostatic energy or dipole energy caused by the point charged atoms.
Since we worked on single graphene layer, hence the van der Waal forces between the layers
were not considered. For our calculations it is quite suitable as we were mainly interested in
the structural changes in the graphene layer and the change in angles which can be accurately
predicted by this software. For a complicated large structure it may not be suitable.
The growth of graphite occurs mainly in the a-direction and infrequently in the c-direction
perpendicular to the basal plane but can occur under certain circumstances. The binding
between the basal planes or graphene layers is very weak during the growth; however, when
trace elements are incorporated into the graphene layers, many types of lattice defects are
formed, such as vacancies and C-ring defects, which results in bending and twisting of the basal
plane. C ring defects are the formation of pentagonal ring (forms curvature), heptagonal ring
and high order ring (disturbs the linking between graphene layers). This process results in
bending or distortion of the basal plane due to the different electronic configuration of the trace
elements compared with that of carbon, which might create a possibility for cross link
formation of the basal plane in the c-direction, as shown in Fig. 32. The HRTEM images
showed that the distance between the basal planes of graphite is different in nodular, vermicular
and flake graphite. If so, then the density of nodular graphite would be slightly different than
that of flake or vermicular graphite.
The analysis is based on the nature of covalent bonding and the bond energies of the trace
elements with an atomic size similar to that of carbon. Table 2 (suppl. 4) lists the type of
bonding and resulting angles after the attachment of trace atom to the pentagonal C ring.
51
Table 12: The effect of foreign atom on the bond angle of a pentagonal ring of C atoms in a graphene.
Pentagon: ~108o, Hexagon: ~120o, Heptagon: ~128o and Octagon: ~135o.
Strongly electronegative atoms possess higher bond energies with C, such as H, N, O and the
halides; however, due to the type of bonding and bond lengths, these atoms exhibit different
effects on the graphite basal plane. The atom sizes, bond lengths, bond energies and
electronegativity between C and various elements are provided in supplement 4 (Table 4).
The reason of choosing a pentagonal ring was that it has the lowest energy to form. By
examining Table 12, one can find a relation between a foreign trace element and the resulting
C ring structure afterward. Some elements results in angle which can promote hexagonal and
high order ring structure while other are producing angles which are promoting pentagonal ring
structure. However mostly we obtain a mix of C ring structure, such as for S, Se, B, P.
Depending on the strength of the bond and the dominate C ring structure, the resulting graphene
structure will be affected accordingly.
In Fig. 30, a comparison is provided between hexagonal and pentagonal ring structure by their
energies. Pentagonal ring structure is easy to form, however when a graphene, having
hexagonal ring structure, after relaxation gets the lowest energy. This is what happens in the
production of nanotubes (CNTs). Literature survey shows that different elements have affected
CNTs in or another way. In a 100 % pure environment, we should expect to form multi wall
CNTs or rods (resulted by wrapping of a graphene or graphene layers around the axis, causing
52
steps) as we have seen in our results for ultra-pure base iron melt. Pentagonal ring structure
when simulated further by attaching C atoms to it, can get a curvature shape which can be
closed to form a dodecahedron sphere. If many such dodecahedron are attached together or if
we continue the growth of one dodecahedron, then it would result in a large sphere as shown
in Fig. 31. This could be the initiation of a spheroidal graphite.
Figure 30. Hexagonal and pentagonal network in a graphene layer and the resulting energy, angles of the
network.
Figure 31. Spheroidal graphite formation from the combination of dodecahedrons formed by pentagonal
rings.
As we see in the Fig. 31, the large sphere seems to grow in branches radially outward. When
this structure reaches to a few nm size, the growth rate of the tips or branches would increase
due to decreasing temperature and increased precipitation, might result in star like growth of
graphite. This has been observed in our result after ion etching on sample T640. If any of the
trace elements are absorbed in the growth direction of the graphite crystal or a C cluster with
53
54
Figure 32. Defects induced into a single basal plane of graphite after adding or substituting a foreign atom in/to the lattice, while assuming
only hexagonal C rings and un-saturated edges, by using Avogadro Software [17]. C ring defect in the basal plane of graphite having
vacancy which could be resulted in with or without external atoms attachment. Side views of the graphene is denoted by arrows with ‘a’ and
‘c’ letters, showing a- and c-plane.
various morphologies for the crystal. The effect of each element on a graphene layer will be
analyzed and discussed in relation to the experimental results. In addition to the analysis of
the trace elements, the effect of vacancies on the structure of a graphene layer was
investigated.
Nitrogen can easily replace carbon in the basal plane due to the small difference in atom size.
This change will not produce any straining effect, as the energy of the graphene layer is at
minimum after relaxation, as shown in Fig. 32. Due to sp2 bonding, the N site will be saturated,
and growth in the c-direction could be difficult; however, pentagonal ring formation is favored,
which can result in curvature in the basal plane. Overall, nitrogen is the element that has the
smallest effect on the graphite morphology and can be considered as a neutral trace element
The study of B-C bonds and sizes suggests that C-B has a comparable bond energy to that of
C-O. The C-B bond length is much shorter than the C-C bond length, which causes strain in
the lattice and creates a curvature of the basal plane. The boron-doped basal plane of graphite
has a higher energy than that with oxygen (after relaxation), as illustrated in Fig. 32. B does
not introduce any vacancies or strong polarity, unlike oxygen. Thus, B favors flake morphology
with branching.
Sulfur can form multiple bonds (from 1 to 6) with C atoms, with various arrangements of atoms,
as illustrated by the examples in Fig. 32. When S atoms are incorporated in the growing
graphene layer, at least one double bond (C=S) will be present in the basal plane, and two single
bonds may be present on one side or both sides of the graphene layer (c-direction, Fig. 32). In
the latter case, one can connect two basal planes with a covalent bond, thus reducing the
distance between the basal planes and favoring growth in the c-direction. The energy of the
graphene layer will increase to a higher value due to the strong double bond and larger atom
size of the S atom, which can decrease the flexibility of the monolayer because of straining
(Fig. 32). Sulfur can introduce pentagonal, hexagonal, heptagonal and sometimes octagonal
rings into the basal plane of graphite (Table 2). This result might occur at a higher concentration
of S in the samples exhibiting the bending effect. When two or three sheets are bonded together
by covalent bonding, their toughness will increase and they can resist bending and folding, thus
stabilizing the flake morphology. Another interesting observation is that the S atoms,
independent of the bonding type (single or double), are always placed in the basal plane, which
stabilizes the flake morphology.
Selenium (similar to sulfur) can form multiple bonds and can share all of its valence electrons
with carbon atoms (Fig. 32). The electronegativity difference between C and Se is 0.1, which
is the smallest difference among the trace elements (after sulfur). Similarly, Se can be bonded
with C in the same manner as sulfur by promoting a combination of pentagonal and hexagonal
rings. The strong bonding (C=Se, approximately > 470 kJ/mol) and shorter bond length (1.1 Å)
strongly affect the lattice by introducing strain into the lattice, thus increasing the energy of the
graphene layer to a higher value (shown in Fig. 32), which increases the toughness and favors
faster growth in the basal plane of graphite.
Phosphorous does not have the same effect on the graphite morphology as oxygen. P can share
5 of its valence electrons by simultaneously establishing bonds with 1 to 5 neighboring C atoms
and forming single and/or double covalent bonds (Fig. 32). Compared with S, the bonding
between C-P is weaker, and the graphene layer attains a lower energy after P is added (Fig. 32).
55
P can induce polarity in the basal plane, which introduces dipole-dipole interactions. The bond
angle between P and C is such that it can promote hexagonal and heptagonal rings together
with pentagonal rings in the graphite basal planes, which stabilizes flake graphite but not to the
extent of S. This result is due to the weaker bonding and polarity in the lattice (Table 3, 4).
Polarization in the basal plane causes bending and twisting locally, which enables the graphene
layer to minimize its energy to balance all types of forces. A graphene layer with lower energy
will not stabilize flake growth effectively.
Figure 33. Demonstration of the growth of C-atoms along the c-plane, caused by the attachment of
traces out of the basal plane and C-ring defects, vacancies, by using Avogadro software. The edges of
the graphene layers are unsaturated. Letters ‘a’ and ‘c’ with arrows shows growth along a- and c-
plane of the graphite.
56
Fluorine, due to single covalent bonding with C, introduces defects into the basal plane;
however, due to its bonding along the c-plane, fluorine could keep two basal planes (locally)
apart. This effect causes non-linearity and un-stability in the flake graphite, where vacancies
and C-ring defects combine with the addition of a F atom, which creates a larger distance
between the two layers. F will introduce a large bumpy or wavy surface due to its highly polar
nature and saturated sites, which might initiate the growth of a new basal plane; thus, growth
in the c-direction would be possible (Fig. 33). The similar would be possible for H atoms as
well.
Oxygen can have single or double covalent bonding. Oxygen has a slightly higher single bond
energy with C than a C-C bond, whereas the C=O bond energy is almost twice as large as the
C-C bond energy. This difference might affect the graphite structure. The oxygen atom is often
placed outside the graphene layer, either above or below the basal plane, which will cause
growth in the c-direction, as illustrated in Fig. 33. Defects will be introduced in the C-ring
structure. There will be a dipole-dipole interaction between the basal planes, which can become
dominant over the van der Waals forces. Oxygen can produce a larger ring structure in the basal
plane together with a pentagonal ring (Fig. 33), resulting in a higher possibility of the formation
of vacancies. In the presence of vacancies, the oxygen atom can rotate and re-orient itself to
balance the interatomic forces and the induced polarity. This process increases the possibility
of graphene bending and twisting. If the oxygen is single bonded between two graphene layers,
it can hold the graphene layers firmly together, thus growth in the c-direction would be possible.
If more than two (C-O-C) bonds are established, the two graphene sheets will resist bending.
Locally, the growth morphology of the graphite will be flake type, which causes the formation
of short graphite flakes, as commonly observed when a high oxygen content is present (in the
complete absence of S). The C=O bond will always cause a dipole moment out of the plane,
which can keep two basal planes far apart due to its saturated site, thus introducing a larger
hump in the basal plane. Such defects in the basal plane will hinder further growth of the flake
graphite in a plane. Instead, different directions of growth will occur or twisting and bending
can occur, which can promote branches of the graphite and growth in the c-direction, as
illustrated in Fig. 33 (A2-O).
Lattice defects such as vacancies are always formed in the basal planes of graphite. These
vacancies increase the graphene energy; however, bending allows the graphene to reduce the
energy and adopt a minimum-energy structure. During very fast cooling of cast iron liquid,
small size spheroidal graphite or a fraction of undercooled fine graphite is formed, regardless
of the normal sulfur concentration in the liquid of grey iron. In rapid cooling of a melt,
numerous vacancies will be present in the graphite crystal. These vacancies will result in
numerous deformities in the form of bending and twisting in the basal plane, which will de-
stabilize the flake growth. The defects result in a possibility of cross growth between the basal
planes. This result is due to the edge effect caused by the vacancy or the presence of a
pentagonal ring in the basal plane with or without trace elements, as illustrated in Fig.
33.
57
4.4.1. Graphite crystallization
Most authors agree that the growth occurs along the basal plane in the a-direction and that the
growth perpendicular to the basal plane is very limited. Recently, Amini et al. [75] suggested
that growth could occur in the c-direction at high undercooling or cooling rates due to a
roughening of the graphite/liquid interface. These authors suggested that this was the reason
for the formation of rod type graphite crystals. The formation of rod type graphite is in our case
related to the composition of the graphite. Rod type graphite formation is favored in pure alloys
due to the high oxygen and nitrogen content in the melt. The melt composition in terms of trace
elements can change during the solidification because of micro-segregation, which can affect
the growth of graphite, depending on the dominant amount of trace element in the melt.
Careful analysis of the rod surface indicates that the surface is built by a bent basal plane. The
crystallization of the rods still occurs in the a-direction; however, the basal planes are bending
during the growth process due to the formation of the lattice defects and oxygen absorption in
the carbon lattice. From the lattice structure viewpoint, as discussed earlier, the presence of a
pentagonal C-ring in the basal plane due to the formation of lattice defects or the incorporation
of some trace elements can cause curvature and folding. If more pentagonal C-rings are present
in the basal plane, the angle of the cone would be sharper.
Most of the publications about the growth of flake graphite agree that the growth occurs in the
a-direction. Many researchers have explained the formation of flakes being due to a decrease
of the surface tension between the liquid and the graphite due to the absorption of sulfur and
the surface active elements on the basal plane. The absorption requires a diffusion process to
the interface, which appears to be a slow process. Theoretical analysis provides another
explanation. S atoms as well as P and Se are trapped in the basal plane and stabilize this plane
by covalent bonding. A high concentration of these elements in the melt can cause bending of
the basal plane due to a strain effect, but cross-linking may still be present between the basal
planes. The growth of graphite nodules in cast iron has been discussed by many researchers.
The ideal growth of nodules with the help of screw dislocation. It is commonly accepted that
the radial growth occurs in the c-direction but that main growth occurs by the tangential growth
of steps in the a-direction. Certain atoms such as O when trapped in the basal plane and bound
to a carbon atom outside the basal plane can constitute a new basal plane (Fig. 33). This result
also occurs when lattice defects are formed, which enables the basal planes to cross link with
each other. In this manner, growth in the c-direction will occur, and steps will be formed on
the surface. The fraction of steps is related to the solidification rate, the content of trace
elements and the formation of lattice defects. A larger content of trace elements and C-ring
defects results in more steps being formed and a more uneven interface with the liquid. At
larger fractions of defects in the graphite lattice, the growth will more unstable, spheroidal
growth will break down and vermicular or exploded types of graphite structure will be formed.
The reason that spheroidal graphite is obtained in fast cooling of a liquid is the lack of time for
the S atoms to become incorporated in the graphene layer. Undercooled graphite consists of
flake morphology locally; however, in the presence of defects (vacancies and foreign atoms
such as O and halides), the graphite cannot preserve the morphology and grows with various
type of morphologies.
58
4.5. Graphite growth control in nodular cast iron
From our analysis it was found that there were many nano sized MgO, MgS and CaO particles
in the matrix. These are the one which are nucleated at the last stages of solidification as a
result of homogenioous nucleation. These particles, oxide or sulfide may not have nucleated
graphite but they have significant role in modifying the graphite morphology towards nodular
growth, by controlling the oxygen and sulfur content in the melt. This phenamena is explained
in the schematic diagram in Fig. 34, where different possibilities of how S and O content can
change and the corresponding changes that are occuring in the graphite growth morphology.
In first case (a) (Fig. 34) where the inoculants are taking part in nucleating new oxides or
sulfides, O and S content both are getting rich into the liquid from very low levels (VL – S/O)
to low levels (L – S/O) and then succeeding towards high levels (H – S/O) and very high level
(VH – S/O). This is an example where it was assumed that VL – S/O and L – S/O does not
influence the graphite morphology and the graphite growth occurs in the nodular form, but at
H – S/O levels the growth transition in the graphite has just been started. At VH –S/O levels
the transition in the graphtie growth is now fully driven by these elements and if one do not
controll it, it can succeed to obtain flake growth mechansim at the end. In the second case (b)
it is shown that what happens if only oxygen in controlled by forming oxides but not sulfur. In
the case (c) the graphite morphology has remained nodular till the end by forming oxides and
fulfides follows it. In the case (d) the growth gorwth morpholology can become slightly
compacted if O and S content are not controlled at early stages; however late nucleation of
oxides and sulfides can once again modify the growth morphology of graphite. Not only one
have to control the sulfur content but also oxygen has to be controlled and that result is shown
in case (e) where only sulfides are formed. If the intial oxygen content at the start of
solidification is slightly higher than the previous cases, may be due to less amount of added
inoculants, the growth morphology of graphite can become random at the early stages of
solidification due to late formation of oxides and sulfides which later modifies the growth
morphology of graphite towards rounded shape, shown in case (f). In the case (g) the formation
of oxi-sulfide particles are shown and how it can maintain the nodular growth of graphite till
the end. If the initial oxygen content at the start of solidification (case h) is high then the growth
of graphite can become as chunky graphite if O and S content is not controlled earlier in the
solidification; however at the end of solidification the growth morphology of the newly
nucleating graphite could be nodular when new oxides and sulfides are formed. High level of
both O and S could result in almost flake graphite if O and S content is not controlled at the
beginning as shown in the case (i). In the last case but not the least, the growth morphology of
graphite could easliy become almost chunky graphite or large comacted graphite if the initial
oxygen content is at very high levels, although S content could be very low at the beginning.
This happens when the inoculants does not have strong de-oxidizers and the Mg treatment was
not effective.
59
60
Figure 34. Schematic representation of the effect of inoculants (de-oxidizers and de-sulfurizes) on the graphite morphology transition during solidification. VL
– S/O, L – S/O shows very low sulfur/oxygen and low sulfur /oxygen respectively and does not influence the graphite morphology. H –S/O shows high
sulfur/oxygen content at which the transition of morphology starts in the graphite growth. VH – S/O shows very high sulfur/oxygen content at which the graphite
morphology is strongly affected. Other terms in the figure such as “Oxd.” means oxide and “Sfd.” means sulfide. White region in the figure represents liquid
(L) and light gray is solid (S).
61
Figure 34. Schematic representation of the effect of inoculants (de-oxidizers and de-sulfurizes) on the graphite morphology transition during solidification. VL – S/O,
L – S/O shows very low sulfur/oxygen and low sulfur /oxygen respectively and does not influence the graphite morphology. H –S/O shows high sulfur/oxygen content
at which the transition of morphology starts in the graphite growth. VH – S/O shows very high sulfur/oxygen content at which the graphite morphology is strongly
affected. Other terms in the figure such as “Oxd.” means oxide and “Sfd.” means sulfide. White region in the figure represents liquid (L) and light gray is solid (S).
4.5.1. Thermodynamics of inoculants
Inoculants, which normally contain Ce and Ca or Sr together with Al or Zr alloyed with Fe-Si,
are often added after the Mg treatment. In the situation when the melt is pre-treated with Mg,
certain elements such as Al and Zr may not be able to nucleate their oxides due to the low O
content in the melt. However, if the inoculation could be performed either before Mg treatment
or together with Mg treatment, then those elements which are relatively less reactive such as
Al and Zr could also form their oxides due to the high initial oxygen content in the melt. The
nucleation sites would increase, and consequently, the S and O contents would also decrease
further compared with the first case when the inoculants were added after the Mg treatment.
This effect was observed in the experimental results. Also when a melt is treated first with
inoculants which contains Ca and Ce, would control the S content immediately and the Mg
treatment afterward would be more effective.
Figure 35. Thermodynamic equilibrium concentration and supersaturated concentration of O with different
inoculation elements while assuming surface of the oxide particle with a decreasing pattern from 0.75 J/m2 at
1450 oC to 0.5 J/m2 at 1200 oC,. The amount of el elements were assumed as Si= 4 %, Al= 0.23 %, La= 1e-
4 %, Sr= 3.5e-4 %, Ce= 1e-4 %, Mg= 0.007 % and Ca= 1e-4 %.
In nodular iron production, after Mg treatment, the oxygen concentration decreases, and it
becomes impossible for some oxides to nucleate homogeneously. By adding FSM and
inoculants at ~1425 °C, the oxygen will decrease to very low levels to establish an equilibrium
between MgO formation and oxygen. The shaded region shows that in the beginning, due to
Ca, Sr, or Ce like elements, the oxygen concentration will decrease at once but it is possible
that some MgO and other type of oxides (Al2O3, SiO2 or ZrO2) will dissolve back and the
oxygen level would rise up back to a level where there is an equilibrium between MgO and O
(Fig. 35).
62
In some cases, for instance when Al2O3 is already nucleated before Mg treatment at σ <1 J/m2,
during FSM treatment, Mg will interact with Al2O3 and can form a compound “MgO.Al2O3”
particle. In the microanalysis, Al2O3 was found together with MgO in many nodules. Cerium,
however, can form a stable Ce2O3 particle at the time of inoculation; but, Mg can deoxidize the
particle and form either only MgO or a compound “MgO.Ce2O3” particle.
Figure 36. Thermodynamic equilibrium concentration of S with Mg, Ca and Ce. The amount of elements were
assumed as Mg= 0.003 %, Ca= 0.0009 % and Ce= 0.0009 %.
The sulfur content in the melt is normally 10 to 100 times larger than the dissolved oxygen in
the melt. There is a higher probability of sulfur interacting with Ca, Ce or Mg-like elements
than O. It is difficult to correctly estimate how much Mg can form its sulfides and oxides. To
simplify the problem, we can assume that the remaining S quantity just before solidification is
equal to the equilibrium value of MgS with S. These observations indicate that CeS will appear
first and then CaS and finally MgS could be formed (Fig. 36), with the composition of the melt
discussed.
4.5.2. The effect of inoculants on the activity of oxygen with MgO
Fig. 37 illustrates the changing of the oxygen level in the melt during inoculation and FSM
treatment. In the first case, during FSM treatment, the oxygen level decreases to the nucleation
limit of MgO and then to point 3´, where there is an equilibrium with MgO. In this case, some
Mg would be consumed according to the mass balance. The second path in Fig. 37 is the case
when Ce-containing inoculants are added before FSM. During this addition, the oxygen content
will reduce to point 2´ and then to 3´. Now, if we add FSM, the oxygen content is low enough
63
for MgO to nucleate; hence, Mg will mostly remain in the liquid unreacted, which can be used
to nucleate new oxides during solidification.
The experiments in series 1 demonstrated that vermicular graphite was formed at the start of
the eutectic reaction. This finding might indicate that the oxygen level is not low enough to
form nodules, which might either be the result of a too low Mg content or MgO was not being
formed. One explanation for this result is tested in Fig. 38.
Figure 37. The effect of sequence of adding Mg and Ce, on the oxygen level at 1420 oC.
In Fig. 38, it is shown that with increasing or decreasing contents of Ca, Ce, Al, Si and Mg, the
equilibrium oxygen with MgO is changing (eq. 2). Due to strong interaction of Ca with O, the
change in equilibrium between MgO and O is significant. Si does not have considerable effect
however Al can influence that result quite allot. At much higher concentrations of Mg, the
equilibrium value between oxygen and MgO rises up which might cause problems for nodular
type of graphite.
𝑓𝑂 = (𝐶𝐶 ∗ −0.35) + (𝐶𝑆𝑖 ∗ −0.14) + (𝐶𝐴𝑙 ∗ −2.81) + (𝐶𝐶𝑎 ∗ −475) + (𝐶𝑀𝑔 ∗ −20) +
(𝐶𝐶𝑒 ∗ −6) …….…2
4.5.3. The formation of complex compounds and oxygen level
Two types of complex oxides could be formed, MgO.SiO2 and MgO.Al2O3. The latter has often
been observed in the centre of the nodules. Afterward, the oxygen concentration decreases to
a level where there is an equilibrium with the complex oxide. This situation could cause the
formation of the chunky and vermicular types of graphite. MgO is formed late during the
solidification process, which reduces the oxygen level to a lower value. MgO particles can
effectively nucleate graphite nodules.
64
Figure 38. The effect of varying composition of Mg, Ca, Ce, Al and Si on the equilibrium value of MgO with
oxygen, due to change in the interaction parameters of O and Mg. Only one elements was considered variable at
a time and all other were kept constant at 0.23, 2.22, 0.001, 0.001, 0.05 wt. % for Al, Si, Ca, Ce and Mg,
respectively.
Figure 39. The oxygen level required for equilibrium and nucleation of MgO and complex compounds of Mg
at 1420 oC
65
4.5.4. During solidification
During solidification, inoculants, oxygen and sulfur enriches the remaining liquid. At a certain
solid fraction, the solubility product of the inoculant with oxygen or sulfur might yield the
required concentration limits for homogeneous nucleation, resulting in new oxide/sulfide
particles. Depending on at which solid fraction they are nucleated and their amount, the
graphite morphology will be affected accordingly, as shown in the schematic diagram in Fig.
41. In the beginning, nodules are formed, but as the liquid was obtaining a smaller volume,
elements starts enriching into the liquid, another type of graphite would grow. The nodules
formed earlier would soon get encapsulated in austenite. After the graphite gets disconnected
from the liquid, then further growth would be controlled by diffusion which will not alter the
morphology. As the solid fraction reaches higher and higher, there would be a possibility to
form new oxides/sulfides particle which would reduce the oxygen and sulfur levels to minimum.
Thus resulting in nodular growth morphology of graphite and graphite would grow on the
newly nucleated oxide particles, as shown in Fig. 41.
It is possible to form MgO multiple times at different solid fractions, as observed in Fig. 40.
The possibility to form MgO.SiO2 instead of MgO was discussed earlier. In that case, the initial
oxygen quantity would be much higher, and the formation of MgO can start at an early stage
of solidification; however, the Mg content might not be sufficient to de-oxidize the melt
properly. During this time, the graphite morphology would most likely be of the vermicular
and chunky type. The formation of the sulfide particle during solidification depends on the
initial concentration of S and the amount of Mg dissolved in the melt. MgS can also form
multiple times at the end of solidification, which might affect the transition in the graphite
morphology.
Figure 40. Homogeneous nucleation of MgO during solidification
66
Figure 41. Schematic of solidification process in four steps.
67
4.6. Graphite growth morphologies in high Al cast iron: SiAl
Al is known as flake graphite stabilizer, which makes the nodularization un-effective. Using
the Mg treatment, graphite morphology was changing towards chunky graphite with increasing
Al content. With the help of thermodynamics, we will try to understand this type of behaviour.
It was shown earlier that a low oxygen content is very important for the formation of nodules,
and MgO particles are needed to nucleate graphite nodules. In Fig. 42, it is shown that with
increasing Al content in the alloy, the equilibrium between oxygen and deoxidizers (Si, Mg,
Ca, Ce etc.) trends towards a higher concentration of oxygen, which is due to the decrease in
the interaction coefficient of oxygen with the mentioned deoxidizers by using eq. 2 (section
4.5.2), for the interaction co-efficient of oxygen in the melt.
Figure 42. The effect of Al content in the melt on the equilibrium concentration of oxygen with Mg, Ce,
Ca, Sr and Si. The oxygen concentration in equilibrium with MgO and Ce2O3 is shown at 4 % and 2 %
Si.
In equation 2, interaction co-efficient of oxygen is largely influenced by the concentration of
Al in the melt. This change in activity of oxygen decreases with increasing Si content in the
melt compared to Al, as shown in Fig. 42, for the formation of MgO and Ce2O3. When both Al
and Si contents are high in the alloy (as it is in our case), then the oxygen level in the melt will
remain high. In this case either one have to increase the amount of inoculants or chose the one
which have strong de-oxidizers. It was found that with an increasing Si content in the melt, the
equilibrium value of MgO with O is not strongly influenced (Fig. 42); however, the
combination of both high Si and Al affects the activity of the oxygen, which makes the
nucleation of MgO in the melt difficult. During solidification (from approximately 1250 °C to
1150 °C) the remaining liquid will be enriched with O, Mg, Ca, Ce, Si and C, but the Al content
will decrease in the melt. The oxygen level required for nucleating MgO is much higher (Fig.
43) compared to alloys with low Si and Al contents.
68
The possibility of forming complex oxides, such as MgO.Al2O3.SiO2, Al2O3.SiO2, MgO.SiO2
etc., was analysed in Fig. 44. According to the available oxygen concentration in the melt,
which is in equilibrium with Al2O3, it is not possible to form complex oxides prior to
solidification; however, during solidification, oxygen enrichment in the remaining liquid can
increase the oxygen concentration to a limit where MgO and/or complex oxides of
MgO.Al2O3 could form (Fig. 44).
Figure 43. Nucleation of oxide particles and the initial level of oxygen prior to solidification.
Figure 44. Equilibrium of oxygen with complex oxides, homogeneous oxides and available
oxygen concentration.
69
CHAPTER 5
CONCLUDING DISCUSSION
Supplement 1 Supplement 2 Supplement 3

Effect of Oxides and MnS on Effect of S and Al on the Graphite growth morphologies in
Topics
the graphite morphology in gray austenite growth morphology cast iron

cast iron and LHIV measurement
To study the effect of oxides,  To study the effect of Al and S  Study of graphite structure
 Any influence from S and O on
Objectives
various inoculants and S on the on the austenite growth

flake graphite nucleation and morphology and finding and the graphite morphology and to
growth morphology comparing different techniques get an explanation to the graphite
of austenite volume fraction and morphology transition
LH measurement
Alloys with different S level Alloys with different S level  Alloy preparation
Quenching Slow cooling  Use of pure Mg, Ca and Sr.
Methods
Slow cooling Thermal analysis  Ion polishing and ion etching

Micro analysis Colour etching  Micro analysis
Thermo-dynamics  Thermo-dynamics
HF* furnace HF furnace HF furnace
DSC** DSC DSC
IR*** Pyrometer DTA FEV-SEM
Tools
SEMI-EDXII LOM InLense detector

LOMIII SEM Gatan PEC’s VI
Gatan Ion slicer
Sequential nucleation of  Austenite volume fraction  Circumferential growth
graphite increased with Al mechanism in nodular graphite
Oxides nucleate MnS and then  With high S, rate of formation  Star like growth from the centre
Major Results
graphite flakes of austenite increased of graphite nodule

Oxides modifies the MnS  Austenite volume fraction  With Mg, Ca and Sr, the
growth morphology from depended on the graphite de-oxidation and de-sulfurization
irregular to regular one. morphology efficiency was different
New oxides can be nucleated  Total LH and LH of eutectic  Presence of micro and nano sized
during the solidification which increased with high S MgO and MgS particles with and
can provide nucleation sites for without connection to graphite
MnS and graphite flakes nodules and flakes
 MnS nucleated graphite flakes  Austenite growth morphology  The transition in graphite
 MnS should nucleate just before depends on S and Al content morphology occurs due to the
the solidification starts and the number of nucleation change in composition of the melt
 Oxides should be nucleated sites for austenite dendrites, in in term of S and O and inoculants
prior to MnS nucleation in the cast iron controls the S and O level in the
melt and during solidification  Higher Al content causes larger melt
 The graphite morphology volume fraction of austenite.  Mg have medium potency of
depends on the S content in the  High sulfur content increases
Conclusion
deoxidizing and de-sulfurizing

alloy the rate of formation of the melt, while Sr have high
 S content equal to or higher austenite potency of only de-oxidizing the
than 0.06 causes thickening of  LH is not a constant property in melt; however Ca have both
the flakes and large MnS cast iron but it rather depends strong potential of de-oxidizing
particles are nucleated on the graphite morphology and de-sulfurizing the melt
 MnS growth morphology which is controlled by the S  The nucleation of nodules can
depends on the oxides level in the alloy only happen at very low S and O
 LH of eutectic is increasing content
with increase in S content.
70
Supplement 4 Supplement 5 Supplement 6
Effect of trace elements on the Graphite growth control in nodular Graphite growth
Topics
graphite growth morphology in cast cast iron morphology in high Al
iron cast iron
 To study the graphite growth  To test the effect of inoculation  Study of graphite
Objectives
morphology transition in pure melts sequence, inoculation temperature on morphology in the

 How trace elements are affecting the the nodularity and nodule count presence of high Al and
growth morphology of graphite at the  How to control the formation of non- to explore the reasons
initial stage of graphite growth nodular graphite of less effective Mg
treatment in this alloy
 Preparing ultra-pure Fe-C alloy  Alloy preparation  Alloy preparation
 Addition of trace elements separately  Inoculation at different temperature  Use of different
to the melt and sequence of adding them inoculants
Methods
 Deep etching  Nodular and nodule size distribution  Different procedures of

 Thermal analysis  Deep Etching inoculation
 Micro-analysis  Deep etching
 Thermo-dynamics  Micro-analysis
 Thermo-dynamics
 HF furnace  vacume furnace  Vacume furnace
 DSC  HF furnace  HF furnace
 DTA  LOM  Colour etching
Tools
 FE-SEM  Colour etching  SEM-EDX

 InLense detector  SEM-EDX  LOM
 FIBVII
 HRTEMVIII
 Each of the above mentioned  Inoculation and Mg treatment at  Al promotes flake
elements have different effect on the lower temperature give better results graphite morphology
Major Results
graphite morphology  Inoculation prior to Mg treatment is  Ca and Ce containing

 HRTEM shows the change in more effective inoculants gives better
lamellar spacing in the different  Ca and Ce containing inoculants nodularity
graphite gives better nodularity than the other  Mg treatment is un-
morphologies ones effective
 Flake graphite have higher LH than  Oxides are the one nucleate graphite
nodules nodules
 Trace element causes defects into the  Inoculation and Mg treatment at  Due to high Al content,
basal plane of graphite by getting higher temperature results in low the interaction co-
covalently bonded in the graphene nodularity and nodule count efficient of O reduces
layers, which affects the graphite  Inoculation prior to Mg treatment to a very low value
growth morphology gives better result than the one which which rises up the
 The inter lamellar distance in the are treated after the Mg treatment equilibrium value of O
graphite was decreasing in the  Strong de-oxidizers and de-sulfurizer with Mg
Conclusion
presence of flake stabilizing trace are more effective to produce nodular  Si segregates positively
elements graphite towards the melt, in the
 Defects and vacancies either  Graphite morphology depends on the presence of high Al
generated from the trace elements or S and O content in the melt during content.
by the cooling rate, causes the growth solidification  It is difficult to reduce
of graphite along the c-plane  The formation of complex oxides oxygen to very low
 The most common defect which could results in higher oxygen level value with Mg unless
prohibits the ciromferencial growth  The interaction co-efficient of oxygen Ca containing
mechanism of graphite is O, which is largely influenced by Mg, Ca, Ce inoculants are used
causes spiral growth and random and Al
growth mechanism in the graphite
* : High Frequency
IV : Latent Heat
** : Differential Scanning Calorimeter
V : Field Emission
*** : Infrared
VI : Precise Etching and Coating System
I : Scanning Electron Microscope
VII : Focussed Ion Beam
II : Energy Dispersive X-ray
 VIII : High Resolution Transmission Electron Microscope
III : Light Optical Microscope
71
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On the Inoculation and Graphite Morphologies of

Haji Muhammad Muhmond

Supplement 2: Literature servey, preparing alloys, preparing experimental setup, experimental

Supplement 3: Literature servey, preparing alloys, preparing experimental setup, experimental

Supplement 4: Literature servey, preparing alloys, preparing experimental setup, experimental

Supplement 5: Literature servey, preparing alloys, preparing experimental setup, experimental

Supplement 6: Literature servey, preparing alloys, preparing experimental setup, experimental

Ductile Cast Iron: Compacted Cast Iron:

Figure 1: Different types of Cast Iron

(d) (e) (f)

MATERIALS AND EXPERIMENTAL METHODOLOGY

2.1 The effect of MnS and Oxides on Graphite Morphology

Table 4. Un-inoculated samples melted in a differential scanning calorimeter (DSC) at a cooling

Table 5. Experiments and experimental conditions.

Table 6. Investigated alloys composition.

2.4 Effect of trace elements on the transition of graphite growth morphology

Table 7: Compositions of the investigated alloys (Fe-balance).

2.5 Graphite growth control

Table 8. Composition of the inoculants used in the experiments

3.1. The effect of MnS and oxides on graphite morphology

Inoculated samples demonstrated a significant reduction in the size of MnS inclusions,

MgO and MgS particles

All MgO particles.

3.3.2. De-oxidation of the melt using pure Ca.

No addition 1 wt. % FeO addition

Figure 17. Sr Treated sample, ion etched sample.

3.3.4. Star like growth mechanism in the nodular graphite

Figure 22. Statistical analysis of the graphite particles in the samples

4.1. Relationship between inoculants and MnS in gray cast iron

Figure 26. Homogeneous nucleation of MnS during solidification.

Figure 27. Homogeneous nucleation of SrO during solidification.

Figure 40. Homogeneous nucleation of MgO during solidification

Supplement 1 Supplement 2 Supplement 3

the graphite morphology in gray austenite growth morphology cast iron

various inoculants and S on the on the austenite growth

Slow cooling Thermal analysis  Ion polishing and ion etching

SEMI-EDXII LOM InLense detector

graphite flakes of austenite increased of graphite nodule

deoxidizing and de-sulfurizing

morphology transition in pure melts sequence, inoculation temperature on morphology in the

 Deep etching  Nodular and nodule size distribution  Different procedures of

 FE-SEM  Colour etching  SEM-EDX

graphite morphology  Inoculation prior to Mg treatment is  Ca and Ce containing

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[15] T. Skaland, AFS Trans., vol. 105, pp. 77-88, 2001.

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[36] T. Carlberg and H. Fredriksson, “Influence of Si and Al on the solidification of cast

[37] N. Kayama, K. Nashimoto and K. Suzuki, “Effect of SiO2 on primary austenite

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[67] N. N. Aleksandrov and N. I. Klochnev, Technology and Properties of Heat-Resistant

[68] Y. G. Bobro, “Aluminum Cast Irons,” Charkovskogo University, 1964.

[69] W. J. Keep, M. C. F and L. D. Vorce, American Association for the advancement of