Morphological Characterization of Primary Austenite in Cast Iron

LICENTIATE THESIS
Morphological Characterization of
Primary Austenite in Cast Iron

Juan Carlos Hernando
Department of Materials and Manufacturing
SCHOOL OF ENGINEERING, JÖNKÖPING UNIVERSITY
Jönköping, Sweden 2017
Licentiate Thesis
Morphological Characterization of Primary Austenite in Cast Iron


School of Engineering, Jönköping University
SE‐551 11 Jönköping, Sweden
Juan‐[email protected]

Copyright © Juan Carlos Hernando

Research Series from the School of Engineering, Jönköping University
Dissertation Series No. 23, 2017
ISBN: 978‐91‐87289‐24‐8

Published and Distributed by
School of Engineering, Jönköping University
SE‐551 11 Jönköping, Sweden

Printed in Sweden by
Ineko AB
Kållered, 2017

ABSTRACT
Automotive industry products portfolio includes a wide variety of complex‐shaped
cast iron products, such as truck engine components, that need to withstand a
constant trend of higher demands, especially urged by stricter environmental
regulations on emissions. Combined with this continued demand on properties
improvement, cast iron industry faces a process problem related to the lack of
understanding of solidification and mechanisms behind defect formation.
Casting products are highly affected by the product design and the manufacturing
method itself, which governs the final microstructure and hence the final mechanical
properties. Wall thickness of the moulding material strongly influences the
solidification time, varying the microstructural coarseness, resulting in a component
with different properties depending on the local shape of the casting.
The main objective of this work is the characterization of the primary austenite
microstructure and its coarsening process, which has been poorly documented in
cast iron literature, to allow the prediction and control of these microstructural
features present in the casting.
The microstructural evolution of the primary austenite in hypoeutectic lamellar
graphite iron (LGI) is studied under isothermal coarsening conditions. The dendritic
microstructure suffered major morphological changes that included dendrite
fragmentation, globularization, and coalescence. Empirical relations based on
morphological parameters are introduced to predict the microstructural evolution of
primary austenite. A novel technique for colour‐etching and semi‐automatic image
analysis for the characterization of quenched dendritic microstructures in cast iron
is presented. A new experimental technique for production of graphitic iron with
varying nodularity is presented as a solution to control the production of compacted
(CGI) and spheroidal graphite iron (SGI) under laboratory conditions. The nodularity
evolution is controlled as a function of the holding time and the residual Mg, allowing
the study of the primary solidification and primary microstructures of hypoeutectic
CGI and SGI in future investigations.

Keywords: Lamellar Graphite Iron, Solidification, Primary Austenite,

Microstructure Evolution, Dendritic coarsening, Compacted Graphite Iron,
Magnesium Fading, Nodularity.

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ACKNOWLEDGEMENTS
I would like to express my sincere gratitude to:
My supervisor Attila Diószegi, for giving me this opportunity, his trust, guidance,
support and extensive knowledge on cast iron. For his endless scientific curiosity, a
continuous source of inspiration for my work.
Björn Domeij, for his friendship, support, and appreciated advice and discussions.
Daniel González, for his friendship, enthusiasm, and help with the experimental work.
Toni Bogdanoff for his altruistic and enthusiastic help and technical assistant.
Caterina Zanella for her valuable help, and fruitful discussions.
Ehsan Ghassemali for his valued assistance and comments.
Paula García‐Caro, Carlos Martínez‐Lage and José Manuel Amieva for their
contribution in the experimental work.
Lucian Vasile Diaconu for his support and assistance during the experimental
castings.
Jörgen Bloom for his assistance during the experimental castings.
Esbjörn Ollas, Peter Gunnarsson and Lars Johansson for their work on the
experimental equipment, and help in the workshop.
Salem Seifeddine and Vasilios Fourlakidis for their good advice over these years.
All my colleagues and friends at the department of Materials and Manufacturing and
at the School of Engineering.
Vinnova for financially supporting the projects CastDesign and Spofic II.
All the involved industrial partners Scania CV AB, Volvo Group AB, SinterCast AB, and
Swerea SWECAST, for their valuable support and contribution to this work.
My beloved family for their constant love and support. Especially to Bea for her
endless inspiration, patience, and love.
Jönköping, April 2017
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SUPPLEMENTS
The following supplements constitute the basis of this thesis:
Supplement I J.C. Hernando, A. Diószegi; An Overview of Isothermal

Coarsening in Hypoeutectic Lamellar Cast Iron.
Presented at TMS 2015, March 15th‐19th, Orlando,

Florida, USA. Published in Advances in the Science and
Engineering of Casting Solidification, John Wiley &
Sons, Inc. (2015): pp. 295‐302. Reprinted by Springer
International Publishing (2016): pp. 295‐302.
J.C. Hernando was the main author. A. Diószegi contributed with advice regarding
the work.
Supplement II J.C. Hernando, E. Ghassemali, A. Diószegi; The

Morphological Evolution of Primary Austenite During
Isothermal Coarsening.
Manuscript. Submitted for journal publication.
J.C. Hernando was the main author. E. Ghassemali assisted with EBSD analysis. A.
Diószegi contributed with advice regarding the work.
Supplement III B. Domeij, J.C. Hernando, A. Diószegi; Quantification of

Dendritic Austenite After Interrupted Solidification in
a Hypoeutectic Lamellar Graphite Iron.
Metallography, Microstructure, and Analysis, 2016, 5,

28‐42.
B. Domeij was the main author. J.C. Hernando designed and assisted during
experimental work, analysis of results and advice regarding the work. A. Diószegi
contributed with advice regarding the work.
Supplement IV J.C. Hernando, B. Domeij, A. Diószegi; Influence of Ti

and Mo additions on the isothermal coarsening
process of primary austenite in Lamellar Graphite Iron.
Manuscript. Abstract accepted for presentation at the

5th Decennial International Conference on
Solidification Processing, Old Windsor, UK, 25th‐28th
July 2017.
J.C. Hernando was the main author. B. Domeij helped with experimental work,
analysis of results and advice regarding the work. A. Diószegi contributed with
advice regarding the work.
Supplement V J.C. Hernando, B. Domeij, D. González, J.M, Amieva, A.

Diószegi; New Experimental Technique for Nodularity
and Mg Fading Control in CGI Production on
Laboratory Scale.
J.C. Hernando was the main author. B. Domeij helped with experimental work,
analysis of results and advice regarding the work. D. González and J.M. Amieva
helped with experimental work. A. Diószegi contributed with advice regarding the
work.

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TABLE OF CONTENTS
CHAPTER 1INTRODUCTION ............................................................................................................................ 1
1.1 BACKGROUND .............................................................................................................................................................................. 1
1.2 CAST IRON ..................................................................................................................................................................................... 1
Carbon equivalent ................................................................................................................................................................. 3
Classification ........................................................................................................................................................................... 3
1.3 CAST IRON SOLIDIFICATION ................................................................................................................................................. 5
Primary solidification .......................................................................................................................................................... 5
Eutectic Solidification .......................................................................................................................................................... 9
1.4 STATE OF ART .......................................................................................................................................................................... 10
Gap between previous research and the present study .................................................................................... 10
CHAPTER 2RESEARCH APPROACH ............................................................................................................. 13
2.1 PURPOSE AND AIM ................................................................................................................................................................. 13
2.2 RESEARCH DESIGN ................................................................................................................................................................. 13
Research perspective........................................................................................................................................................ 13
Research questions............................................................................................................................................................ 14
Research strategy ............................................................................................................................................................... 15
2.3 MATERIAL AND EXPERIMENTAL PROCEDURE ......................................................................................................... 16
Materials ................................................................................................................................................................................ 16
Experimental procedure ................................................................................................................................................. 16
2.4 CHARACTERIZATION............................................................................................................................................................. 20
Sample preparation ........................................................................................................................................................... 20
Colour etching ..................................................................................................................................................................... 20
Microstructure evaluation .............................................................................................................................................. 20
Microstructural quantitative characterization of the coarsening process ................................................. 21
Graphite Characterization .............................................................................................................................................. 22
CHAPTER 3SUMMARY OF RESULTS AND DISCUSSION .......................................................................... 23
3.1 CHARACTERIZATION OF COARSENING PROCESS OF THE PRIMARY AUSTENITE .................................... 23
Qualitative description of the coarsening process of the primary austenite ............................................ 23
Quantitative characterization of the coarseness of the primary austenite ............................................... 26
Novel characterization technique for dendritic austenite in quenched samples .................................... 31
Modification of the coarsening process of the primary austenite by alloying ......................................... 31
3.2 NODULARITY AND MG FADING CONTROL IN CGI AND SGI PRODUCTION .................................................... 33
Effect of holding time on nodularity .......................................................................................................................... 33
Effect of holding time on cooling curves .................................................................................................................. 35
Effect of holding time on chemical composition ................................................................................................... 35
Effect of holding time on residual and free magnesium .................................................................................... 36
Relation between magnesium fading and nodularity ......................................................................................... 36
CHAPTER 4CONCLUSIONS .............................................................................................................................. 39
CHAPTER 5FUTURE WORK ........................................................................................................................... 41
REFERENCES .................................................................................................................................................... 43
APPENDED PAPERS ............................................................................................................................................ 49
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CHAPTER 1
INTRODUCTION
CHAPTER INTRODUCTION
The purpose of this chapter is to introduce the reader to some important definitions
and concepts related to cast iron alloys that will be used in the following chapters.
The chapter starts with a small introduction on cast iron alloys and continues with a
short description of their solidification process.
1.1 BACKGROUND
Casting is one of the oldest manufacturing methods for producing complex shapes for
applications ranging from decorative parts to engineering components. Based on a
solidification process, casting remains one of the most important commercial
processes for many materials[1], with an increasing global production during the last
6 years, where global economy almost stagnated [2]. Cast parts can be found in
approximate 90% of manufactured goods and equipment [3], including critical
components for aircraft and automobiles, home appliances and medical equipment.
Iron casting have been known and used for more than 2500 years [3]. The wide range
of mechanical and physical properties of cast iron, associated with its competitive
price, makes cast iron a very important engineering material with numerous
technological applications. Present in a wide variety of parts, we find cast iron in
general machinery pieces, railroad accessories and many other elements. One of the
largest users of cast iron is the automotive industry, using cast iron to manufacture
engine blocks, cylinder heads or piston rings among many other components [4].
1.2 CAST IRON
The term cast iron refers to the multicomponent Fe‐C based alloys that solidify with
an eutectic solidification and usually contain more than 2 wt.% of C. Using this
definition we can easily distinguish cast irons and steel, which has a lower carbon
content and solidifies according to the metastable Fe‐C diagram, while cast iron
solidifies on the stable Fe‐C diagram shown in Figure 1 [5].
The eutectic point on this Fe‐C binary diagram is assumed at 4.3 wt.% C. Cast irons
with C content below 4.3% are hypoeutectic irons and the solidification will start with
the crystallization of the austenite phase. On the contrary, cast irons with a C content
above 4.3% are hypereutectic irons and the solidification starts with crystallization
of graphite. In both cases, the solidification process ends below the eutectic
temperature, where the eutectic reaction occurs and the remaining liquid transforms
into austenite and graphite.
Commercial cast iron alloys include, however, the addition of several chemical
elements in the composition. Alloying elements are added to the melt to control the
1
solidification process and change the properties of the material. The main alloying
element is Si, usually in a content between 1 to 3 wt.%. Si promotes the solidification
according to the stable Fe‐C diagram having a strong graphitizing effect [6], increases
the difference between the higher eutectic solidification temperature of the stable
diagram compared to that of the metastable diagram [7], increases fluidity and
reduces hardness and shrinkage [8]. Due to this strong influence, some authors even
consider cast irons as ternary Fe‐C‐Si alloys.
Cast iron alloys contain many other minor alloying elements depending on the
required properties. Common elements found in cast irons with engineering
applications are P, S, Mn, Ni, Sn, Cu, Cr and Mo.
Some of these alloying elements, such as S, Al, Sn or Cu, are known as graphitizers for
their ability to promote the formation of graphite by reducing the solubility of carbon
in the eutectic iron‐carbon melt. On the other hand, elements such as, Ca, Mn, Mo, Ti
or Cr retain carbon in the form of iron carbides forming metallic carbides in the
solidification process. These elements are known as carbide stabilizers [7].

Figure 1: The stable binary Fe‐C phase diagram. Calculated with Thermo‐Calc 2016b and TCFE7
database [9].
2
Carbon equivalent
The concept of carbon equivalent (CE) is used in cast iron to account for the effect of
the alloying elements on solidification regarding the eutectic reaction. CE is defined
considering the amount of carbon, silicon and phosphorus as main elements affecting
the eutectic reaction [10]:
1 1
CE %C %Si %P 1
3 3
Accounting the effect of these elements on the solidification process, CE is used,

instead of the single C content, to define hypoeutectic or hypereutectic compositions.
Despite its general use in foundry practice, it must be noted that the same CE can
result on different properties depending on many other factors, such as the rest of
alloying elements or different cooling conditions.
Classification
Nowadays, the most extended way to classify cast irons is by specifying the dominant
morphology of the graphite phase in the microstructure. The morphology of the
graphite determines three main families [3, 11]:
‐ Lamellar graphite iron (LGI), where the graphite adopts the shape of lamellas
or flakes. This type of iron is also known as grey iron.
‐ Spheroidal graphite iron (SGI), where the predominant graphite shape is
spheroidal, also called graphite nodules. This variety is also referred as to
nodular iron.
‐ Compacted graphite iron (CGI), where the graphite particles adopt an
intermediate compacted worm‐like shape, also called vermicular graphite.
Another possible classification criterion is based on the dominant phase formed in
the metallic matrix after the eutectoid transformation, e.g. ferritic or pearlitic iron.
(a) (b) (c)

Figure 2: Principal graphite forms in cast iron materials: (a) lamellar graphite (LG), (b) spheroidal
graphite (SG), and (c) compacted graphite (CG) [12].
3
(a) (b)
Figure 3: Microstructures of cast iron samples under optical microscopy after subjected to a colour
etching process with Motz’s reagent showing: (a) spheroidal graphite (SG) and compacted graphite
(CG) surrounded by ferrite, and (b) lamellar graphite (LG) in a pearlitic matrix.
The graphite morphology confers different physical and mechanical properties to the
three main families of cast iron alloys. For instance, SGI has higher mechanical
properties favoured by the nodular particles, while LGI has good thermal properties
due to the sharp graphite particles. CGI as a transitional behaviour, due to the
intermediate character of the vermicular graphite shape, shows an excellent
compromise in thermal and mechanical properties.
Different methods have been used to characterize the different industrial grades
among the main cast iron families. Nowadays, due to the existing image analysis tools,
the concept of nodularity is widely applied by cast iron users and industry and it is
defined by various standards, e.g. ASTM [13] and ISO [14]. Nodularity uses the
concept of the roundness of the graphite particles, defined as:
4
Roundness ∗ 2
Where A is the area of the particle and is the area of a circle with a diameter
equal to the maximum distance between two boundary points of the particle, .
Graphite nodules are those graphite particles with more than 0.625 roundness,
considering intermediate particles those with a roundness between 0.525 to 0.625.
Measuring the roundness of every graphite particle viewed on a two‐dimensional
polished surface, the nodularity is calculated by ISO according to:
∑A 0.5 ∗ ∑ A
Percent Nodularity 100 ∗ 3
∑A
The classification according to ISO standard is that CGI should have less than 20%
nodularity with no presence of lamellar graphite particles.

4
The classification of LGI is based on the lamellar graphite distribution in the

microstructure. The different distributions are named from A to E and are
schematically represented in Figure 4 [12]

Figure 4: Different graphite distribution types in LGI [12].
1.3 CAST IRON SOLIDIFICATION
Solidification is the phase transformation from liquid to solid. During this

transformation, the atoms in the melt start to rearrange from short‐range order in
the liquid phase to regular positions on a crystallographic lattice. The atoms need to
release energy in order to rearrange [15, 16]. This energy is released in the form of
extracted heat via the surrounding walls of the mould.
The final microstructure and thus the properties of cast irons are highly influenced
by the metallurgical conditions during the solidification. Chemical composition,
modification treatment, inoculation, cooling rate and atmosphere in the furnace are
some of the variables that influence the final casting properties [3, 16, 17].
Primary solidification
The solidification process of a hypoeutectic cast iron alloy can be divided into two
different events: the primary solidification and the eutectic solidification [3, 4].
1.3.1.1 Nucleation of primary austenite

According to the thermodynamic equilibrium diagram, the primary solidification
starts below the liquidus temperature with the nucleation of the primary austenite.
Nucleation requires certain undercooling in the melt for the creation and growth of
nuclei with a critical radius. The higher undercooling will facilitate an easier event of
nucleation. The maximum undercooling observed at commercial castings is not
sufficient to trigger a homogenous nucleation event and therefore, all nucleation
events during cast iron solidification are assumed as heterogeneous [3, 17]. The
presence of impurities and the surface of the mould wall are preferential sites for the
nucleation of the primary austenite. After the mould filling, the mould wall is the
coldest part of the system and can generate the sufficient undercooling for the first
nucleation to take place.
It has been demonstrated that the effectiveness of a compound acting as substrate in
heterogeneous nucleation is related to the lattice disregistry between the nucleating
agent and the nucleated phase [18]. On that sense, the most effective nucleating agent
for primary austenite should be pure iron particles as they have the same crystal
structure [19]. Other compounds acting as effective nucleants for austenite
precipitation are silicon carbide (SiC) [19], or graphite in the case of hypereutectic
5
irons [20]. Despite the large lattice disregistry with austenite, silicon dioxide powder
(SiO2), was also found to be an effective inoculant [21].
1.3.1.2 Growth of primary austenite

The stable nuclei of austenite continue to grow in the form of dendrites, known as
primary grains or primary crystals [22, 23]. The dendrites are composed by a main
arm (primary arm) that branches into lateral arms (secondary arms and tertiary
arms) if the distance with neighbouring dendrites is sufficient [15].

Figure 5: Schematic representation of a dendrite [4].
The primary crystals will first grow favourably oriented to the heat extraction,
perpendicular to the mould wall towards the centre of the casting and forming a
structural region known as columnar zone [1]. This columnar grow will form the
skeleton or skin of the casting which has great influence on defect formation [24].

Figure 6: Schematic representation of columnar dendritic growth from the surface of the mould. The
dendrite grains are form by one dendrite per grain. All dendritic arms within a dendrite have a
unique crystallographic orientation [17].
Additionally, equiaxed crystals will be nucleated on impurities floating in the melt if

the critical undercooling is reached ahead of the columnar growth. Growing in six
orthogonal directions, due to the anisotropy of the face centred cubic crystal of the
6
austenite, these crystals constitute the second growth type and will create a region in
the casting known as the equiaxed zone [25]. Each of these crystals is formed by a
unique dendrite of the same crystallographic orientation [15, 22]. Both types of
growth occur until the austenite dendrites impinge on each other and block their
growth, reaching the dendritic coherency, defining the final macrostructure of the
casting [26]. Dendritic coherency doesn’t occur simultaneously throughout the full
macrostructure but during a time interval.

Figure 7. Binary Fe‐C‐Si phase diagram at 1.8% Si, obtained using Thermocalc® with the TCFE6
database (left). Typical cooling curve and the schematic illustration of the solidification process and
structure (right) [27].
1.3.1.3 Coarsening of primary austenite

After the macrostructure of the casting is defined, when dendrite coherency is
reached, the main growth mechanism for the primary dendritic structure consists on
a coarsening process.

Figure 8: Micrograph of a coherent dendritic microstructure in the liquid‐solid region in cast iron.
The coarsening process, also known as Ostwald ripening, is a diffusion controlled

phenomenon that minimizes the interfacial free energy of a liquid‐solid system. The
initial dendritic structure is not in thermodynamic equilibrium due to its large
interfacial area [28]. This diffusional process includes dissolution and reprecipitation
7
of the solid phase making the overall length scale of the system increasing and the
total interfacial area decreasing [29]. This mass diffusion process is associated with
the curvature dependence of the equilibrium concentration, represented by the
Gibbs‐Thomson equation (4) [28]:
where C is the composition of the liquid at the solid‐liquid interface, C is the

composition at the flat interface, is the capillary length, which is dependent on
material parameters and H is the mean interfacial curvature.
Coarseness of dendritic structures is commonly described in cast iron literature in
terms of the secondary dendrite arm spacing (SDAS) shown in Figure 6 [4, 15, 30, 31].
However, it has been shown in other alloys, that severe morphological changes might
occur during the dendritic coarsening process [32]. The smaller arms are re‐melted
at expenses of the large ones [33], proceeding with a dendritic fragmentation [34].
The dendritic structure is no longer existing and the detached particles adopt a
globular shape [35]. Furthermore, these globular particles will eventually coalesce
into a larger globular particle to minimize the interfacial area per volume [36]. Under
these conditions, the application of SDAS to represent the coarseness of the
microstructure is not applicable and other shape independent parameters have been
introduced in the literature [32, 37].
Previous investigations have introduced the study of the evolution of primary
austenite under dynamic coarsening during the sequence of solidification of
hypoeutectic LGI [37]. In these conditions, the continuous precipitation of solid phase
until the end of solidification, first during the primary solidification and later during
eutectic solidification, does not allow a thorough study of the evolution of the
dendritic microstructure, which is influenced on its development by the eutectic
precipitation. A common solution to solve this problem applied in the investigation
of other alloys is the study of the coarsening process under isothermal conditions
[38].
(a) (b)
Figure 9: Three‐dimensional reconstructions of coarsened Al–Cu samples: (a) 10 min and (b) 3
weeks [38].
The effect of several alloying elements, such as B, Ti, Zr, Al and Bi, have been reported
to have certain influence on the primary solidification and the primary dendrite
morphology of hypoeutectic grey cast iron. Previous works suggested a significant
refining effect on the austenite promoted by these elements [23, 39‐41]. However,
8
the characterization of the microstructural coarseness was described more on

qualitative terms, such as “short”, “random” and “loosely packed”, rather than on
quantitative measurements.
Eutectic Solidification
During dendritic growth, the interface composition of the austenite follows the
liquidus line in the Fe‐C diagram shown in Figure 1, resulting in the rejection of the
excess of carbon to the melt. Once the liquid reaches the eutectic composition and the
required undercooling for its nucleation, the eutectic phase precipitates. In this
eutectic phase, carbon precipitates as graphite. The eutectic solidification also starts
with a nucleation event followed by a growth process.
1.3.2.1 Nucleation of graphite

The nucleation of graphite, assumed heterogeneous, occurs on pre‐existing
inclusions in the liquid [42‐46]. For lamellar graphite, these inclusions are complex
sulfides (Mn,X)S that previously nucleated on complex oxides of Al, Si, Zr, Mg and Ti
[42, 43, 46]. On the other hand, it has been observed that spheroidal and compacted
graphite have similar nucleation sites [11]. These nuclei are formed by complex Mg
silicates (MgO.SiO2) that nucleated on the external layer of MgS and CaS sulfides [44].
1.3.2.2 Growth of graphite

The subsequent growth of graphite nuclei, determining the graphite morphologies
presented in Figure 2 is primarily affected by two factors: the presence of surface
active impurities in the melt, and the cooling rate during solidification of the alloy [3].
The effect of higher cooling rates is accepted to be promoting the formation of SGI.
The influence of impurities can be divided into two categories [3]:
a) reactive impurities, promoting SGI formation such as Mg, Ce, Ca, Y, and La,
called compacting or spheroidizing elements,
b) surface‐active impurities, which favour LGI formation, such as S, O, Al, Ti, As,
Bi, Te, Pb, and Sb, called anti‐compacting or anti‐spheroidizing elements.
The presence of these impurities affects the principal growth direction of graphite
[47, 48]. In the case of LGI, dominant growth takes place along the A‐axis, while in SGI
it occurs along the C‐axis. An intermediate situation takes place for CGI, since
dominant growth direction continuously varies between the A axis and the C axis [47,
48].

Figure 10. Hexagonal structure of graphite showing possible growth directions a and c [49].
9
The surface‐active impurities are absorbed on the prismatic face of the hexagonal
graphite lattice, creating a non‐faceted interface, that requires low driving forces to
grow, i.e. low undercooling, e.g. the case of LGI, while for SGI the growth on the faceted
interface requires larger undercooling [11, 43, 45].
Reactive impurities are then added to the melt to scavenge the reactive impurities,
specially O and S, and control graphite morphology in a nodularization treatment [3,
11]. The most common element used to this purpose is Mg, but Ce or RE metals are
also used for this treatment [11]. The main purpose of this treatment is to reduce the
oxygen activity in the melt, by formation of oxides, and control the graphite shape
during solidification [50, 51].
The main problems associated to this nodularization treatment, that hinder the
accurate control of the graphite morphology are:
a) the narrow window to produce CGI treatment over time: the abrupt
transition in terms of Mg content from CGI to LGI is complex to control during
production of CGI components, as shown in Figure 11 [52].
b) the fading of the nodularization treatment during production: Mg content
fades over time if the melt is held at elevated temperatures [53]. Several expressions
and different values for the fading rate of Mg with respect to time are reported in
literature [53‐58].

Figure 11: Nodularity values depicted as a function of total Mg content. Vertical lines show the
narrow CGI production region [52].
1.4 State of Art

Gap between previous research and the present study
From the literature review above it can be seen that we have acquired an extended
knowledge on cast iron over the last decades, however, there are still several aspects
and problems that remain unsolved in its solidification process. These are translated
into daily problems for producers and user of cast iron. One of the research gaps that
is identified, is the limited number of works studying the influence of the primary
solidification, and primary austenite on the subsequent solidification process and
final properties of the material.
10
The transformation of austenite during the eutectoid reaction, occurring around

730˚C, makes its characterization at room temperature not possible under a normal
solidification process. Only etching techniques allow the observation of the former
primary austenitic structures in the as cast microstructure [59, 60]. Special
experimental techniques, like interrupted solidification experiments, are required to
preserve the primary austenite at room temperature [61]. The characterization of the
primary austenitic macrostructure is also complicated, where experimental
treatments are required to partially retain the primary austenite, and reveal the
primary grain structure [19, 22]. These experimental limitations hinder the
investigation of the primary austenite since they are not available techniques for all
researchers on the field. On the contrary, the presence of graphite is revealed after a
basic polishing process. This fact promoted a great advance on the knowledge front
on the eutectic solidification stage in cast iron, which was deeply studied by
numerous researchers [42, 43, 45, 48, 62‐66].
Some researchers have investigated the growth characteristics of the primary phase,
which has been demonstrated to influence the eutectic cell size, defining its final
microstructure [67]. The dynamic coarsening of primary austenite in LGI has been
recently measured in interrupted solidification experiments and correlated to the
eutectic phase fraction and size scale [68]. On the same trend, recent results correlate
the coarseness of the primary austenite to the mechanical response of the material
[37] and the existence of defects such as shrinkage and metal expansion penetration
[69, 70].
The major influence of the graphite in the properties of cast iron can never be ignored,
but only promoting the front knowledge on the primary solidification to the same
level, and clarifying its influence on the final microstructure, will allow a full
optimization of the properties of cast iron components.
This study tries to enhance the knowledge on the primary solidification in LGI
characterizing the mechanisms of the coarsening process of the primary austenite in
LGI, responsible for the final morphology of the primary microstructure and thus
related to the final properties. The evolution of the primary austenite during
solidification, reported in the literature as subjective qualitative descriptions,
requires quantitative parameters and empirical relations for its prediction.
At the same time, the study of the primary solidification on CGI and SGI remains
poorly understood due to the limitations during production presented in this
literature section. This work aims to present the required experimental tools to
extend the study of the primary solidification to CGI and SGI hypoeutectic
composition in future steps of this research.
11

12
CHAPTER 2
RESEARCH APPROACH
This chapter describes the research methodology used in this thesis. The purpose and
aim of the thesis are first described, followed by a description of the research
materials, research methods, and research activities.
2.1 PURPOSE AND AIM
Automotive industry product portfolio covers an extensive variety of complex‐

shaped cast iron products, such as truck engine components. These components,
need to endure a constant trend on higher demands, especially urged by severe
environmental regulations on emissions.
The product design and the casting process, govern the final microstructure of the
material and hence its final performance. Wall thickness of the moulding material
strongly influences the solidification time, varying the coarseness of the
microstructure, giving result to a component with different properties depending on
the local shape of the casting.
A deeper understanding on the coarsening process of the primary austenite could
improve the ability to predict the formation of some casting defects, such as metal
expansion penetration and improve simulation tools to model the interdendritic
feeding mechanisms after dendritic coherency of the primary austenite.
The aim of this research is to improve the knowledge and characterization tools of
the primary austenite network and its coarsening process, a field that has been poorly
documented in cast iron literature. The intended industrial contribution developed
from this knowledge is to enhance prediction and control of this microstructural
features present in the casting and contribute to an improvement in properties and
reduction of defect formation.
2.2 RESEARCH DESIGN

Research perspective
Research in the discipline of material science is mostly based on deductive reasoning

supported by empirical quantitative data. The use of a deductive reasoning approach
transfers the argument from general principles to particular cases using hypothesis
testing to validate the truth of the conclusion [71]. The research starts with the
statement of the topic of interest and continues with an iterative information
gathering process that will lead to the definition of a hypothesis. This hypothesis will
later be validated or refuted by observations, data collection and analysis to state a
general law based on empirical observations.
13

Figure 5. Schematic representation of the applied research approach [71].
The importance of the literature review is crucial since it will help to narrow down
the possible experimental variables to study, set limitations and identify the last
trends on experimental techniques existing in the research community working with
similar metallic alloys. This information is first retrieved, selected and evaluated. This
process is iterative and it is constantly resumed if new relevant variables, relations
or publications related to the research appear [72]. The information resources used
were mainly online databases (Scopus and Web of Science) that granted access to
journal and conference publications but also resources from Jönköping University
library such as books and e‐books.
The experimental method is the main technique applied throughout this research.
The main objective is to infer causation between solidification variables –such
temperature, time, chemical composition, chemical composition‐ and the coarsening
process of the primary austenite in cast iron.
Research questions
From the previous literature review, the general theory of solidification and the
coarsening process in metallic alloys are studied. From this process is easy to
conclude the technological importance of coarsening process in industrial metallic
alloys. At the same time, there is a lack of literature about this topic of interest in one
of the most important material family of metallic alloys, cast iron alloys which in
contrast with other technical alloys, have received insufficient treatment in this topic
in literature during last decades.
The current research, therefore, tries to extend the knowledge on coarsening of the
primary austenite in both LGI, CGI and SGI, the three main industrial types of cast iron
alloys and tries to answer the following research questions:
1. What are the main mechanisms of coarsening in primary austenite in cast iron?
The coarsening mechanisms of primary austenite in cast iron must be understood in
order to control and predict its evolution.
2. Which are the most suitable parameters to establish a quantitative
characterization of the coarseness of the primary austenite?
The main parameters applied to coarsening characterization in metallic alloys are
related to the solidification time. They should be applied to cast iron investigations
to avoid ambiguous interpretation of the coarsening phenomena
3. Can we modify the coarsening process of the primary austenite through alloy
selection?
Some previous studies shown in the introduction reported an influence of several
alloying elements on the primary austenite. The possibility to influence the
coarsening process by means of alloying elements is also intended to be studied in
this research.
14
Research strategy
In the previous section, it was introduced that the lack of appropriate experimental
techniques and a common characterization terminology are some of the main
problems that hinder the investigation of the primary solidification and primary
austenite.
The purpose of Supplement I and Supplement II is to study the coarsening process of
the primary austenite in cast iron by solving these limitations. The output of
Supplement I is the description of an experimental technique enabling the study of
the isothermal coarsening process and the creation of a qualitative model of the for
this isothermal coarsening process referring to RQ1. Supplement II will include a
quantitative characterization of the process, generating kinetic and morphological
laws for coarsening mechanism in LGI, addressing RQ2.
After that, the experimental technique introduced in Supplement I and II, and the
characterization improvements implemented Supplement III, are applied to the
research problem stated in RQ3. Supplement IV studies the possible modification in
the coarsening process of the primary austenite inferred by chemical composition
variations, i.e. inclusion of alloying elements.
Oriented to improve a similar knowledge on primary solidification and primary
austenite on CGI and SGI solidification, Supplement V presents a novel experimental
technique allowing the production and characterization of CGI and SGI samples under
laboratory condition. The results introduced in Supplements I, II and III will be
applied to the characterization of the coarsening process of the primary austenite in
SGI and CGI.
Figure 12: Schematic research strategy.
15
2.3 MATERIAL AND EXPERIMENTAL PROCEDURE
Materials
The experimental work performed in this thesis involves 8 alloys listed in Table 1.
Material related to Supplements I and II is a hypoeutectic lamellar graphite iron,
noted as Alloy L. The material for Supplement IV consists of 6 alloys with different
contents of Mo and Ti added on a similar base hypoeutectic lamellar graphite iron.
Supplement III is based on one of these alloys, Alloy Mo . Note that the composition
listed here is the correct one and not the one specified in Supplement III. The last
supplement, Supplement V, studies a rather different material compared to the
previous ones and is based on a hypereutectic spheroidal iron, Alloy S.
Alloys L, Mo , Mo and Mo were produced in an industrial foundry, while the rest of
the alloys were produced in an experimental foundry plant. The nodularization
treatment in Alloy S was performed with FeSiMg. The chemical composition of each
alloy listed in Table 1 was obtained using optical emission spectrometry (OES) on a
rapidly solidified coin sample.
All alloys were cast in furan sand moulds, in the shape of cylindrical specimens of Ø50
mm diameter. The cast cylinders were machined to cylindrical specimens of 38 mm
diameter with a weight of 400 ± 0.5 g which yields an approximate height of 42 mm.
Table 1: Chemical composition of the experimental materials. Measured using OES. CE=C+1/3(Si+P)
Alloy CE C Si Mn P S Cu Mo Ti Mg Fe
L 3.9 3.3 1.8 0.58 0.034 0.086 0.9 0.22 ‐ ‐ Bal.
Mo 4.0 3.4 1.9 0.57 0.052 0.089 0.9 0.05 ‐ ‐ Bal.
Mo 4.0 3.4 1.9 0.59 0.053 0.085 0.9 0.48 ‐ ‐ Bal.
Mo 4.0 3.4 1.9 0.60 0.053 0.085 0.9 0.94 ‐ ‐ Bal.
Ti 3.9 3.4 1.5 0.63 0.037 0.025 1.0 ‐ 0.05 ‐ Bal.
Ti 3.9 3.4 1.5 0.61 0.034 0.027 1.1 ‐ 0.15 ‐ Bal.
Ti 4.0 3.5 1.5 0.57 0.034 0.026 1.0 ‐ 0.41 ‐ Bal.
S 4.7 3.9 2.6 0.64 0.030 0.010 0.8 ‐ ‐ 0.065 Bal.
Experimental procedure
The experimental work performed in this work is based on the re‐melting and re‐
solidification of the experimental alloys introduced above. Experiments, however,
can be differentiated in two types, those experiments that study the primary
solidification and the coarsening process of the primary austenite in hypoeutectic
lamellar graphite iron, covered on Supplements I, II, III and IV; and the experimental
work performed to introduce a new technique for production of CGI and SGI under
16
laboratory condition that will allow the implementation of the knowledge achieved
in the previous supplements on the primary solidification in CGI and SGI.
2.3.2.1 Experiments on primary solidification (Supplements I, II, III and IV)

The machined specimens were subjected to a re‐melting process followed by a
cooling process leading to a primary solidification event and a subsequent isothermal
treatment. The whole process was conducted inside a vertical tube electrical
resistance furnace under argon gas atmosphere to preserve the chemical
composition of the alloy.

Figure 13: Re‐melting experimental equipment used in this research work.
The main details of the process can be summarized as follows. On preliminary

experiments, the specimens were introduced into the chamber inside an alumina
crucible and re‐melted in a heating cycle of 90 minutes from room temperature to
1723 K (1450 °C) and held for 30 minutes. The furnace was switched off and
solidification process of the material started. The solidification process was recorded
with two thermocouples for each alloy. One thermocouple was placed at the
17
geometrical centre of the sample and a second one was in the same planar section of
the sample but in contact with the wall of the crucible. The thermal coherency was
identified as the maximum temperature difference between centre and wall
thermocouple prior to eutectic solidification [73], shown in Figure 14 a. This thermal
information allows the design of the isothermal heat treatment to study the
isothermal coarsening process of the primary austenite.

(a) (b)
Figure 14: a) Cooling curve of alloy L and b) isothermal temperature profile for Supplements I and II.
After these preliminary experiments, the same re‐melting program was applied to
the specimens, however, this time the solidification process was halted when the
thermal coherency was reached and an isothermal temperature profile was added to
the program, shown in Figure 14 b, and samples were isothermally coarsened for
different times, resulting in final specimens with microstructure of varying
coarseness. At the end of this isothermal time, the samples were immediately
quenched by being dropped into flowing water to suppress the stable eutectic
transformation and preserve the dendritic structure at room temperature. The
different duration of the isothermal treatments performed on this investigation for
each alloy is listed in Table 2. These time intervals were chosen to promote the full
development of the coarsening process, including long times previously never
studied for cast iron solidification.
Table 2: Duration of the isothermal treatment performed in investigations related to Supplements I,
II and IV
Isothermal coarsening times (in minutes)
Alloy L 0 30 90 180 360 720 1440 2880 4320 5760
Alloys Mo , Mo , Mo 0 30 90 180 360 720 ‐ ‐ ‐ ‐
Alloys Ti , Ti , Ti 0 10 30 180 360 720 ‐ ‐ ‐ ‐
18
The thermocouples used for the preliminary experiments are calibrated type S
(Pt/Pt+10%Rh) mounted in an alumina case which insulates the thermocouple wires,
leaving only the welded joint accessible. The thermocouples are protected by glass
tube to prevent direct contact with the melt. The thermocouples are connected to a
commercial data acquisition system that records all the data measured by the
thermocouple.
2.3.2.2 Experiments on nodularity and Mg-fading control in CGI production

(Supplement V)
The aim of these experiments was to produce graphitic cast iron of the main three
families with controlled graphite morphology, ranging from LGI to SGI. The
experimental procedure was similar to the one previously described for the
experiments of primary solidification. The main difference is that the holding time at
1723 K (1450 °C) was on this occasion varied to represent different initial
solidification conditions in each experiment, and therefore to obtain samples with
varying nodularities at the end of the solidification process depending on the holding
time. The cooling process was continued until room temperature under the same
conditions for all the experiments performed. The experimental set up was slightly
modified from the one used in the previous experiments to introduce the stable argon
gas flow of 4 l/min from the bottom part of the furnace’s chamber. The holding time
was changed in 10 minutes’ increments as listed in Table 3.
Table 3: Duration of the holding times performed in investigation related to Supplement V
Alloys S H0 H10 H20 H30 H40 H50 H60 H70 H80 H90 H100 H110 H120 H130 H140
Holding
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
time (min)
A series of quenching experiments was additionally performed to examine the

chemical composition of the melt after the re‐melting process and before the start of
the solidification process after different holding times, see Table 4. The sample was
re‐melted at 1723 K (1450 °C) and held the correspondent time, but immediately
after the end of the holding time, the sample was quenched into water to promote a
white solidification and avoid graphite precipitation. This experimental series
provided samples suitable for OES.
Table 4: Quenching experiments performed in investigation related to Supplement V
Alloys S Q0 Q10 Q20 Q30 Q60 Q110
Holding time (min) 0 10 20 30 60 110
19
2.4 CHARACTERIZATION
Sample preparation
After all the re‐melting experiments, all the samples produced were sectioned
approximately at their middle section, around 20 mm from the bottom end. Samples
were mounted in thermosetting resin and ground with SiC papers of different
granulometry from a grit size of P80 (FEPA) to P2000 (FEPA) to subsequently start a
mechanical polishing process with solutions containing diamond particles of 3 and 1
µm applied on satin woven acetate and short synthetic nap clothes correspondingly.
For samples requiring graphite characterization, in Supplement V, this standard
process produced a good result regarding graphite retention, but some graphite
particles were partially covered by ferrite and could lead to a wrong interpretation.
To solve this problem an additional polishing step with an oxide slurry was manually
applied for graphite characterization.
Quenched samples produced for chemical composition analysis in Supplement V,
were grounded to produce a flat surface suitable for OES. OES was performed with a
Spectro SPECTROMAXx stationary metal analyzer. A minimum of 3 measurements
per sample were performed.
Colour etching
Samples from Supplements I and II were etched at 381 K (108 °C), for approximately
2 minutes with Motz’s reagent [60], consisting of 10 g NaOH, 40 g KOH, 10 g picric
acid and 50 ml of distilled water. This process made the primary austenite discernible
from the eutectic liquid.
Application of the new tinting technique for quenched samples introduced in
Supplement III [61], made the dendrites distinguishable after additional polishing
steps of 20 seconds with a l µm diamond suspension for samples related to
Supplement IV. This new method supposes a considerable reduction in processing
time and eliminates chemical hazards to the operator compared to the use of Motz’s
reagent.
Microstructure evaluation
The microstructures generated after sample preparation were studied by optical

microscopy (Olympus GX71F). For samples related to Supplement I, micrographs
capturing the whole cross‐section of the specimen were taken.
For samples from Supplement II, III and IV, the colour‐etched micrographs were
transformed into binary images, where dendrites were represented as black colour
objects. A Wacom Cintiq interactive pen display was used for this purpose. Whilst in
Supplement II this operation was done manually, in Supplements III and IV a semi‐
automatic technique was applied with a significant reduction in processing time.
20
(a) (b)
Figure 15: a) Colour etched micrograph from Supplement II and b) its equivalent binary image.
The electron backscatter diffraction (EBSD) analysis of representative samples from

Supplement II, i.e. after 0 min, 30 min, 6h, 24h, and 48 h of isothermal treatment was
carried out by an EDAX detector mounted on a JEOL 7001F scanning electron
microscope. Using an accelerating voltage of 20 kV and a step size of 1 µm, an
approximate area of 0.6 mm × 3.3 mm was scanned for each sample. EBSD maps were
further analysed using TSL‐OIM v.7.3 package.
Microstructural quantitative characterization of the coarsening

process
The microstructure of the samples from Supplements II, III and IV was quantitatively
characterized in terms of stereological relations using Olympus Stream Motion
Desktop software 1.9.1. in the binary images. The main stereological parameters used
in Supplements II, III and IV are: the modulus of primary austenite, M , the specific
inverse surface area, S , of the primary austenite phase and the hydraulic diameter
of the interdendritic phase, D and can be calculated as follows [37]:
M / / 5
S / / 6
D ⁄ ⁄ ⁄ 7
where is the total area of the austenite, is the perimeter of the austenite phase
and the total area measured. The complete mathematical derivation of the
parameters can be found elsewhere [37, 74].
21
The distance to the nearest austenite particle, D , is also characterized. It measures
the distance between the centre of gravity of one austenite particle and the centre of
gravity of all its surrounding neighbours and returns the smallest distance.
For Supplements I and II, SDAS characterization was performed on a minimum of 7
measurements per sample with at least 3 parallel secondary arms per measurement.
The mean value of the mean curvature (H) of the primary austenite particles was also
estimated [75‐77]. To estimate H, a test line must be swept across the planar section
of interest to count the number of interceptions with particles , and the number of
particles per unit area . Then H can be estimated by [78]:
H / 8
Where is the number of interceptions with particles per unit length and not the
number of particles intercepted.
2.4.4.1 Sampling Area

The extent of the area analysed has a direct impact on the reliability of the results.
The smaller the size of the analysed the higher the standard deviation of the
measurements. On a similar investigation [79], is it recommended the selection of a
sampling area based on the coarser microstructure. In the current work, the sampling
area for microstructural characterization is rather high compared to other
investigations. Two areas of 19 mm2 extracted from the central section of each
sample are used for this purpose. Because of the severe microstructural changes
observed at longer coarsening times, an extra area of 19 mm2 was analysed to
improve the reliability of the characterization of the samples coarsened for longer
times. The analysis of such a large area for each sample will provide strong statistical
support for the quantitative analysis.
Graphite Characterization
In Supplement V, the graphite is characterized using the concept of nodularity

described in the introduction section, Equation 3, and applying ISO [14] and ASTM
standards [13]. Microstructural features smaller than 10 µm are considered micro
porosities, defects due to sample preparation or particles that should be excluded
from graphite analysis. Graphite particles in contact with the limits of the image are
not considered in the analysis.
A preliminary analysis of the microstructures revealed a large graphite particle size,
enabling the use of a low magnification, allowing to characterize a much larger
surface area than required in the standards. A minimum of 40 micrographs for each
specimen is used for this purpose, representing a minimum area of 137 mm2 for each
specimen, improving result soundness.

22
CHAPTER 3
SUMMARY OF RESULTS
AND DISCUSSION
In this chapter, the main results of the appended papers are summarised and
discussed. This chapter is divided into main two parts: the characterization of the
coarsening of the primary austenite in LGI, and the description of nodularity and Mg‐
fading control in CGI and SGI production.
3.1 CHARACTERIZATION OF COARSENING

PROCESS OF THE PRIMARY AUSTENITE
The characterization of the coarsening process of the primary austenite in

hypoeutectic lamellar iron comprises the main body of this research work. This topic
is treated in Supplements I, II, III and IV.
Qualitative description of the coarsening process of the primary

austenite
Supplement I approached for the first time the study of the isothermal coarsening of
the primary austenite in cast iron. This research article tries to answer RQ1, using a
qualitative perspective. The lack of cast iron literature in the field made this study
required to foreseen the parameters needed for its quantitative characterization.
The purpose of this article was also to present the experimental technique required
to investigate the microstructural evolution of the primary austenite during primary
solidification of alloy L.
This technique combines re‐melting experiments with the use of thermocouples,
thermal analysis of primary solidification and calculation of coherency to create an
isothermal profile to study the coarsening process, illustrated in Figure 14,
interrupted solidification experiments to preserve the primary austenite at room
temperature, and singular etching techniques to characterize the samples.
The isothermal temperature profile in these experiments was calculated to achieve a
stable temperature of 1448 K (1175 °C) in the centre of the sample. This temperature
is approximately 15 K above the equilibrium eutectic temperature estimated as 1434
K (1161 °C) in a Fe‐C‐Si equilibrium diagram for the chemical composition used in
this work. As aimed, this temperature produced no interaction with the eutectic
reaction. Representative colour etched micrographs of the coarsened samples as a
function of coarsening time are shown in Figure 16. To facilitate the comprehension
and the interpretation of the results, the micrographs in Figure 16 show
23
representative micrographs of the measured areas in Supplement II, belonging to the
same samples.

Figure 16: Representative colour‐etched micrographs of the samples as a function of coarsening
time: (a) 0 min, (b) 30 min, (c) 1.5 h, (d) 3 h, (e) 6 h, (f) 12 h, (g) 48 h, (h) 72 h, and (i) 96 h.
Fragmentation of the dendritic structure over time shows that SDAS is not applicable
for long isothermal coarsening times and new parameters should be used to
characterize the coarseness of the primary austenite.
3.1.1.1 Dendrite fragmentation by EBSD characterization

Although dendrite fragmentation is a well‐known phenomenon occurring during
coarsening, the analysis of the two‐dimensional micrographs presented in Figure 16
cannot provide conclusive evidence of its occurrence in the coarsening process of the
primary austenite. The apparent absence of dendritic structures in the last
micrographs shown in Figure 16, could merely be an artefact of a two‐dimensional
investigation.
24
If dendrite fragmentation is occurring during coarsening, the austenite particles are

expected to have a different crystallographic orientation as the coarsening
progresses due to the likely convection in the liquid. To confirm that dendrite
fragmentation does, in fact, occur during the primary austenite coarsening process,
an EBSD characterization of the coarsened samples was performed in Supplement II.
EBSD maps, showing the crystallographic orientations of the primary austenite and
the cementite phases in the samples coarsened after 0 min, 30 min, 6h, 24h, and 48 h
are shown in Figure 17.
The crystallographic orientations of the primary austenite confirmed a progressive
loss of coherency, dendrite fragmentation and coalescence of the austenite particles.
From the original dendritic structure, showing large austenite grains with a common
crystallographic orientation, shown in Figure 17 a, the progression of the coarsening
process promotes the disappearance of dendritic structures and the crystallographic
orientation of the primary austenite starts to show a variation amongst the austenite
particles as shown in Figure 17 c. The dendrite fragmentation can be confirmed after
24 h of coarsening, Figure 17 d, where globular particles with different
crystallographic orientations are observed in the EBSD map. Figure 17 e shows an
indication of the coalescence of three particles with the same crystallographic
orientation, indicated with arrows.
Figure 17: Inverse pole figures showing the orientation of austenite grains after: a) 0 min, b) 30 min,
c) 6h, d) 24h, and e) 48 h of isothermal treatment (a‐e from top to bottom). RD and RA stand for
Radius Direction and Rotational Axis of the sample, respectively.
25
Observation of the full cross section of the samples combined and the analysis of the
microstructures combined with the EBSD analysis allowed the description of the
coarsening mechanism in lamellar cast iron in Supplement II, shown in Figure 18.
The classic mechanism of dendritic coarsening, occurred over the whole isothermal
treatment, promoting a reduction of the primary austenite surface area. The
progression of the coarsening produced a progressive dendrite fragmentation
phenomenon, leading to a detached distribution of globular austenite particles in the
liquid. From this point, after longer coarsening times, coalescence of detached
particles took place, creating large austenite units.

Figure 18: Schematic representation of the isothermal coarsening process in primary austenite.
Quantitative characterization of the coarseness of the primary

austenite
Supplement II intends to answer RQ2, characterizing the coarseness of the primary

austenite based on the experimental work, results, and observations from
Supplement I.
This work introduces appropriate morphological parameters to characterize the
coarseness of the primary austenite for the whole coarsening process, including
longer coarsening times where dendritic structures no longer exist.
3.1.2.1 Secondary dendrite arm spacing (SDAS)

The SDAS of primary austenite was measured for the samples that showed a dendritic
structure and discernible secondary arms. The loss of dendritic structure and
dendrite fragmentation made that only four samples were suitable for SDAS
characterization. In Figure 19 it can be observed that the SDAS shows a linear
correlation to t1/3. This behaviour is similar to that reported in a previous
investigation in cast iron [79].
SDAS cannot be used to characterize the coarseness of the remaining samples since
the secondary dendrite arms no longer exist. Note that SDAS values shown in
Supplement I for samples Q5 and Q6 are not comparable to those shown in
Supplement II. Values for those two samples were estimated accounting for austenite
particles not belonging to a secondary dendrite arm. The correct values for SDAS are
those included in Supplement II.
26

Figure 19: SDAS as a function of time. Error bars show 95 percent confidence intervals.
3.1.2.2 Stereological estimation of the mean value of the mean curvature

of the primary austenite ( )
Variations in the mean interfacial curvature, H, are responsible for concentration
gradients in the solid‐liquid interface according to Gibbs‐Thomson equation, for
further details see Supplement II. This concentration gradients lead to a diffusive
transport of solute that governs the evolution of the microstructure during the
coarsening process. H is, therefore, a critical parameter to control in order to predict
the evolution of the microstructure.
By application of stereological relations (8) to the binary images of the coarsened
samples in Supplement II, the mean value for the mean curvature, H, of the primary
austenite is estimated. Shown in Figure 20, the evolution of the inverse of H as a
function of coarsening time shows. a linear relation to the cube root of time
throughout the coarsening process. This result was expected since coarsening
proceeds by the increase in the length scale of the regions of low curvature at the
expense of the high curvature regions [29].

Figure 20: Inverse of mean curvature of the primary austenite, H, as a function of time.
27
3.1.2.3 Modulus of the primary austenite phase ( )
The modulus of the primary austenite phase, M , represents the coarseness of the
austenite phase through the relation between the volume of the austenite phase and
its corresponding containing surface. It is, therefore, independent of the shape and
the total sampling volume measured.
Results represented in Figure 21 confirm that the modulus of primary austenite, M ,
successfully describes the reduction of surface area to volume ratio of the austenite
phase and shows a stable linear relation to t1/3 for all the samples.

Figure 21: Modulus of the primary austenite phase, M , as a function of time.
Despite all transformations in the austenite phase during the coarsening process
shown in the previous section, this parameter shows a stable relation to the cube root
of coarsening time, characterizing the coarsening process in a more appropriate way
than SDAS.
M exhibits a constant increase proportional to the coarsening time:
M μm C μ μm min t min 8 5t 9
3.1.2.4 Hydraulic diameter of the interdendritic phase ( )

The hydraulic diameter of the interdendritic phase, D , is a recently introduced
parameter used to measure the interdendritic space existing between the primary
austenite phase [37, 74].
Applied to the coarsening process a linear relation to the cube root of time can be
seen in Figure 22 for the first eight samples analysed, but not for the last two samples
corresponding to longer times.
In the mathematical derivation of D , the total volume of the sample and the volume
occupied by the austenite are considered, making the parameter sensitive to possible
variations in austenite volume fraction. The difference observed in these last two
28
values comes associated with the variation of the austenite volume fraction, i.e. the
austenite area fraction in the two‐dimensional measurements, observed in the
mentioned samples.
Figure 22: Hydraulic diameter of the interdendritic phase, D , as a function of time.
3.1.2.5 Distance to the nearest austenite particle ( )

D measures the shortest distance between the centre of gravity of an austenite
particle and the centres of gravity of all its neighbouring particles.
In contrast to the variation of D , D shows a robust relation to the cube root of
coarsening time, shown in Figure 23, since it is not related to the total volume:
D μm C μ μm min t min 33.7 23.3 t 10
Figure 23: Distance to the nearest austenite particle, D , as a function of time.
29
3.1.2.6 Relation between and and
The evolution of H, fundamental variable to characterize the coarsening process, is
coupled to the shape independent parameters M and D . Both parameters show a
linear relation to H as shown in Figure 24 a) and b). This way the evolution of H can
be predicted with the following empirical laws (11),(12):
H μm C KM μm 10 1.5M 11
H μm C KD μm 8 0.3D 12
The empirical relation between H and D cannot be established according to Figure

24(c).
(a) (b)
(c)
Figure 24: Relation between H and a) M , b) D and c) D .
30
Novel characterization technique for dendritic austenite in

quenched samples
In Supplement III, an unconventional etching technique to reveal the dendritic

microstructure of a quenched hypoeutectic lamellar graphite iron is presented. This
etching technique is based on the application of the last polishing step on a synthetic
short napped cloth with a 1 µm diamond suspension. Additional polishing steps of 20
s, coloured the dendritic uniformly, on a more repeatable and safer process than
picric based colour‐etching methods.
Based on the colour‐etched micrographs, two quantification methods for estimation
of the microstructural parameters are compared: the application of a semi‐automatic
colour selection method on Photoshop combined with the further application of the
image analysis software, and the measurement of the same parameter based on point
counting and line intercept methods. The agreement between the measurements
depended on the coarseness of the measured dendritic microstructure. Some
measurements showed significant systematic disagreement correlated with the
coarseness of the measured dendrites.
Modification of the coarsening process of the primary austenite by

alloying
Once the quantitative parameters to study the coarsening process of primary

austenite had been introduced in Supplement II, Supplement IV tried to elucidate if
the addition of Ti and Mo had any influence on the rate of the isothermal coarsening.
Applying a similar experimental set up to Supplements I and II, the use of the newly
discovered etching technique and novel automatic colour selection technique to
transform the original micrographs into binary images introduced in Supplement III
[61], the coarsening of the primary austenite was studied for alloys Mo , Mo , Mo ,
Ti , Ti and Ti under isothermal conditions.
Results on M , introduced in Supplement II, show no noticeable effect on the rate of

isothermal coarsening of primary austenite.
Although, M , showed a stable linear relation to t1/3 for all the samples in this work,
regardless of the chemical composition and volume fraction measured in the sample,
as shown in Figure 25, confirming its robustness for quantitative characterization of
the whole coarsening process, including the longer coarsening times showing a very
similar empirical relation (13) to that showed in Supplement II (9).
M μm C μ μm min t min 12 4t 13
31

Figure 25: Modulus of primary austenite, M , for Ti and Mo alloyed LGI, versus the cubic root of time.
Error bars show 95% CI.
32
3.2 NODULARITY AND Mg FADING CONTROL IN

CGI AND SGI PRODUCTION
The description of the Mg fading process and the nodularity evolution for SGI and CGI
solidification are covered in Supplement V. These are key factors to consider when
trying to produce CGI and SGI in a controlled manner. They are, therefore, significant
parameters to control in the context of this research, since the knowledge obtained
for LGI solidification intends to be transferred to CGI and SGI solidification in the
future work.
Effect of holding time on nodularity
The experimental series listed in Table 3 was produced by re‐melting a base SGI, alloy
S, with a nodularity of 96 % and varying the holding time at 1723 K (1450 °C). The
effect of varying this holding time gave place to different solidification conditions and
the consequence can be observed in many microstructural parameters.
Micrographs of the samples from the re‐melting experiments are collected in Figure
27. The number of graphite nodules decreases as the volume fraction of compacted
graphite increases with increasing holding time. While transition between SGI and
CGI occurs gradually, the transition between CGI and LGI occurs suddenly. The
appearance of lamellar graphite occurs after 130 minutes of holding time.
From the analysis of the nodularity, shown in Figure 26 we can observe a

proportional decay with the holding time for the SGI region. The rate of deterioration
of nodularity from 60 to 120 minutes slows down, belonging to CGI irons with
nodularity values lower than 20%.

Figure 26: Nodularity evolution as a function of holding time. Circles represent nodularity values
according to ISO 16122 standard and squares represent nodularity values according to E2567 ASTM
standard. Error bars represent the 95 percent confidence interval.
33
Figure 27: Micrographs of the samples resulting from the re‐melting experiments: (a) 0, (b) 10, (c)
20, (d) 30, (e) 40, (f) 50, (g) 60, (h) 70, (i) 80, (j) 90, (k) 100 (l) 110, (m) 120, (n) 130, and (o) 140
minutes of holding time.
34
Effect of holding time on cooling curves
The analysis of the cooling curves recorded during the re‐melting experiments, show
in Figure 28 three types of eutectic solidifications according to the presence of the
three main types of graphite shapes in the final microstructure. The first type consists
of the cooling curves belonging to H10 and H20, with nodularity values of 86 % and
70 %, showing a typical thermal behaviour of an SGI solidification with a high
undercooling and low recalescence rate. When the presence of compacted graphite
starts to be significant in the microstructure, even if the final nodularity values yield
to SGI values, both the undercooling and the recalescence increase. Special mention
deserves the considerable increase in the recalescence rate, as can be seen in the
cooling curve of H40, which final nodularity yields 41 %, far from the CGI values. This
behaviour is repeated for H60, H80 and H100, samples with nodularity values of 14
%, 10 %, and 5 % respectively, all within the CGI range according to ISO standard.
The last group of cooling curves reflects the presence of lamellar graphite in the
microstructure, H130, and H140. The low undercooling and intermediate
recalescence rate are commonly found for LGI solidification.

Figure 28: Representative cooling curves from the re‐melting experiments.
Effect of holding time on chemical composition
The chemical composition of the samples produced in the quenching experiments

listed in Table 4 was measured by OES. Results on the main elements affecting cast
iron solidification like C, Si, S, P, Mn, Cu, and Sn show a stable behaviour over the
holding time. Only Mg is affected by holding time.
In the case of carbon, it could be expected a certain decarburization after holding the
melt at 1723 K (1450 °C) for long times. Results on chemical composition and
measured graphite volume fraction indicate that the Ar‐rich atmosphere inside the
chamber of the furnace avoids the decarburization as intended.
35
Effect of holding time on residual magnesium
Holding time influences the amount of residual magnesium. Shown in Figure 29, Mg
follows a polynomial relation with time in minutes (14). Part of the Mg is lost to the
atmosphere due to its high vapor pressure at this temperature and some due to the
reaction with the small amount of oxygen inside the chamber:
Residual Mg wt % 0.06 0.00088 t 3.6 ∗ 10 t

14
for 0<t<110, where t time in minutes

Figure 29: Residual Magnesium content as a function of holding time. Error bars represent the 95
percent confidence interval.
Relation between magnesium fading and nodularity
Residual Mg and nodularity for CGI and SGI castings can be related by the curve
depicted by Dawson in Figure 11 for 0.013 wt % S [52]. The production window for
CGI establishes 0.006 wt % Mg as lower limit and 0.016 wt % Mg as the higher limit.
On the other hand, the lower limit for SGI production is set around 0.030 wt % Mg
and contents around 0.050 wt % Mg establish the upper limit above which increasing
Mg concentration does not produce higher nodularities. These values are however
linked to several casting parameters like inoculation, oxygen and sulphur content,
cooling conditions, etc. If these conditions change the curve shifts horizontally or
vertically.
Experimental results of this work confirm the same overall trend when representing
nodularity as a function of the residual Mg content, also refereed as total Mg in
literature, in Figure 30. The mentioned figure from literature, based on qualitative
observations [52], and later attempts to describe this relation between nodularity
and Mg levels [58], never proposed a mathematical expression that could allow its
36
modelling based on experimental values. In the present work, a relation is derived,

connecting nodularity, according to ISO standard, to the residual Mg content at the
beginning of the solidification (15).
The regions giving a result to CGI and SGI can be delimited in Figure 30. The residual
Mg limits for CGI production are 0.008 to 0.025 wt % of residual Mg and can be
translated into holding time with (14). The same observation can be done on the SGI
region of the curve where an asymptotic behaviour can be presumed for higher Mg
values than 0.06 wt % of residual Mg.
Nodularity wt % 19.2 2.6 ∗ 10 Mg 1.35 ∗ 10 Mg 1.17 ∗ 10 Mg
15
for 0.0066<Mg<0.065, where Mg in wt %.

(a)
(b)
Figure 30: (a) Nodularity values depicted by Dawson as a function of total Mg content [52], and (b)
Nodularity values, according to ISO 16122 standard, as a function of residual (total) Mg content for
CGI and SGI region in the present work. Error bars represent the 95 percent confidence interval.
37
38
CHAPTER 4
CONCLUSIONS
In this chapter, the conclusions from the present work have been drawn.
The understanding of the mechanisms governing the coarsening process of the

primary structures in cast alloys is of major importance to predict and tailor the final
performance of the material and control formation of defects. This study, introduced
the morphological characterization of the primary austenite during coarsening,
promoting a better understanding of its influence on the subsequent solidification
process. The following conclusions are highlighted from the work:
 A qualitative model describing the different steps of the coarsening process of
primary austenite has been presented. The mechanisms of dendrite
fragmentation and coalescence of primary austenite were successfully proved
by EBSD measurements.
 The shape‐independence of M and D , proven to be related to the mean
curvature of the primary austenite allows the quantitative characterization
and prediction of the full coarsening process of primary austenite.
Experimental temporal laws for the microstructural evolution during
coarsening are presented.
 A novel technique for etching and semi‐automatic image analysis for the
characterization of quenched dendritic microstructures in cast iron has been
presented.
The complete characterization of the coarsening process achieved in this work has
proved that coarsening is the source of major changes in the morphology of primary
austenite. This work intends to increase the awareness on the need of including this
process when creating models of the solidification of cast iron.
The study of the solidification sequence in CGI and SGI is now possible due to the
implementation of the findings in LGI and the development of a new experimental
technique to produce graphitic irons with controlled nodularity. The main
conclusions of this study are:
 Nodularity fading decays linearly to holding time for SGI, while CGI shows a
slower rate of reversion. The transition between SGI and CGI occurs gradually
while transition between CGI and LGI is abrupt.
 The analysis of the cooling curves shows that all the samples with the presence
of compacted graphite show a similar solidification behaviour, regardless of
the final nodularity values.
 Magnesium fading was successfully characterized. The relation between
nodularity and residual magnesium in the melt, quantitatively described on
previous investigations, was quantitatively described using this experimental
technique and a mathematical equation for its modelling is proposed.
39

40
CHAPTER 5
FUTURE WORK
In this chapter, some ideas on how to continue the future work are presented.
There are various directions related to the performed work that can be considered as
future routes to exploit and complement the knowledge acquired in this work. The
findings of this work could be extended in future work by exploring the influence of
the primary solidification in several aspects.
Relation between primary and eutectic solidification
The influence of the primary solidification and the evolution of the primary austenite,
on the eutectic solidification, should be explored. The possibility to study both events
on the solidification in a clear way with the presented technique and elucidate the
relation between nucleation and growth between both phases could provide an
important knowledge to model the complete solidification process, considering the
interactions between size scale of solidification microstructures and material
parameters.
Relation between coarseness of primary microstructure and macrostructure
At the same time, the effect of the primary solidification and the coarseness of its
primary austenite in the macrostructure of the casting should be enlightened to
clarify its possible influence on the primary grain size.
Modification of the coarsening process
Alternative routes to achieve a modification of the coarsening rate should be explored.

The proposed elements could show an influence in the coarsening process by other
means apart from the isothermal process studied in this work, i.e. during dynamic
coarsening.
Primary solidification of CGI and SGI
The application of the morphological characterization techniques presented for the

primary solidification of hypoeutectic LGI should be transferred to hypoeutectic CGI
and SGI to develop a deeper understanding in the challenging solidification sequence
of these materials.
41

42
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47

48
APPENDED PAPERS
Supplement I J.C. Hernando, A. Diószegi; An Overview of Isothermal
Coarsening in Hypoeutectic Lamellar Cast Iron.
Presented at TMS 2015, March 15th‐19th, Orlando,

Florida, USA. Published in Advances in the Science and
Engineering of Casting Solidification, John Wiley &
Sons, Inc. (2015): pp. 295‐302. Reprinted by Springer
International Publishing (2016): pp. 295‐302.
Supplement II J.C. Hernando, E. Ghassemali, A. Diószegi; The

Morphological Evolution of Primary Austenite During
Isothermal Coarsening.
Supplement III B. Domeij, J.C. Hernando, A. Diószegi; Quantification of

Dendritic Austenite After Interrupted Solidification in
a Hypoeutectic Lamellar Graphite Iron.
Metallography, Microstructure, and Analysis, 2016, 5,

28‐42.
Supplement IV J.C. Hernando, B. Domeij, A. Diószegi; Influence of Ti

and Mo additions on the isothermal coarsening
process of primary austenite in Lamellar Graphite Iron.
Manuscript. Accepted for presentation at the 5th

Decennial International Conference on Solidification
Processing, Old Windsor, UK, 25th‐28th July 2017.
Supplement V J.C. Hernando, B. Domeij, D. González, J.M. Amieva, A.

Diószegi; New Experimental Technique for Nodularity
and Mg Fading Control in CGI Production on
Laboratory Scale.
49

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LICENTIATE THESIS

Juan Carlos Hernando

Department of Materials and Manufacturing

SCHOOL OF ENGINEERING, JÖNKÖPING UNIVERSITY

Jönköping, Sweden 2017

Morphological Characterization of Primary Austenite in Cast Iron

Keywords: Lamellar Graphite Iron, Solidification, Primary Austenite,

Juan Carlos Hernando

Jönköping, April 2017

Supplement I J.C. Hernando, A. Diószegi; An Overview of Isothermal

Presented at TMS 2015, March 15th‐19th, Orlando,

Supplement II J.C. Hernando, E. Ghassemali, A. Diószegi; The

Manuscript. Submitted for journal publication.

Supplement III B. Domeij, J.C. Hernando, A. Diószegi; Quantification of

Metallography, Microstructure, and Analysis, 2016, 5,

Supplement IV J.C. Hernando, B. Domeij, A. Diószegi; Influence of Ti

Manuscript. Abstract accepted for presentation at the

Supplement V J.C. Hernando, B. Domeij, D. González, J.M, Amieva, A.

Manuscript. Submitted for journal publication.

1.2 CAST IRON

Accounting the effect of these elements on the solidification process, CE is used,

(a) (b) (c)

The classification of LGI is based on the lamellar graphite distribution in the

1.3 CAST IRON SOLIDIFICATION

Solidification is the phase transformation from liquid to solid. During this

1.3.1.1 Nucleation of primary austenite

1.3.1.2 Growth of primary austenite

Additionally, equiaxed crystals will be nucleated on impurities floating in the melt if

1.3.1.3 Coarsening of primary austenite

The coarsening process, also known as Ostwald ripening, is a diffusion controlled

where C is the composition of the liquid at the solid‐liquid interface, C is the

the characterization of the microstructural coarseness was described more on

1.3.2.1 Nucleation of graphite

1.3.2.2 Growth of graphite

1.4 State of Art

The transformation of austenite during the eutectoid reaction, occurring around

2.1 PURPOSE AND AIM

Automotive industry product portfolio covers an extensive variety of complex‐

2.2 RESEARCH DESIGN

Research in the discipline of material science is mostly based on deductive reasoning

Figure 12: Schematic research strategy.

L 3.9 3.3 1.8 0.58 0.034 0.086 0.9 0.22 ‐ ‐ Bal.

Mo 4.0 3.4 1.9 0.57 0.052 0.089 0.9 0.05 ‐ ‐ Bal.

Mo 4.0 3.4 1.9 0.59 0.053 0.085 0.9 0.48 ‐ ‐ Bal.

Mo 4.0 3.4 1.9 0.60 0.053 0.085 0.9 0.94 ‐ ‐ Bal.

Ti 3.9 3.4 1.5 0.63 0.037 0.025 1.0 ‐ 0.05 ‐ Bal.

Ti 3.9 3.4 1.5 0.61 0.034 0.027 1.1 ‐ 0.15 ‐ Bal.

Ti 4.0 3.5 1.5 0.57 0.034 0.026 1.0 ‐ 0.41 ‐ Bal.

S 4.7 3.9 2.6 0.64 0.030 0.010 0.8 ‐ ‐ 0.065 Bal.

2.3.2.1 Experiments on primary solidification (Supplements I, II, III and IV)

The main details of the process can be summarized as follows. On preliminary

Isothermal coarsening times (in minutes)

Alloy L 0 30 90 180 360 720 1440 2880 4320 5760

Alloys Mo , Mo , Mo 0 30 90 180 360 720 ‐ ‐ ‐ ‐

Alloys Ti , Ti , Ti 0 10 30 180 360 720 ‐ ‐ ‐ ‐

2.3.2.2 Experiments on nodularity and Mg-fading control in CGI production

A series of quenching experiments was additionally performed to examine the

Alloys S Q0 Q10 Q20 Q30 Q60 Q110

Holding time (min) 0 10 20 30 60 110