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Materials Science Forum Vols.

790-791 (2014) pp 458-463

Online available since 2014/May/09 at
(2014) Trans Tech Publications, Switzerland

Graphite Growth Morphologies in Cast Iron

Haji Muhammad Muhmonda and Hasse Fredrikssonb
Materials Science and Engineering department, KTH, Sweden a,b a, b
Keywords: Cast iron, graphite morphology, transition, clusters, micro-segregation, ion etching,
and thermodynamics.

Abstract. Graphite growth morphology was studied by using InLense detector on FEG-SEM after
performing ion etching on the samples. Star like and circumferential growth mechanism of graphite
was observed in the graphite nodules. Pure ternary alloy of hypo eutectic and hyper eutectic
composition was treated with pure Mg, Ca and Sr, to study the effect of O and S concentration in
the melt, on the transition of graphite morphology from nodular to vermicular/compacted and flake
graphite. The change in the melt composition between the austenite dendrites due to microsegregation of S, O and inoculants and their possible effects on the transition of graphite
morphologies as well as the nucleation of new oxides/sulfides particles is discussed with the help of
The transition of graphite morphologies in cast iron from nodular to compacted/vermicular
(CG/VG) and to flake graphite was not fully understood. Strong de-oxidizers and desulphurizer are
often added to cast iron as inoculants which provide nucleation sites for the graphite. Certain
elements such as Ca, Mg, La and Ce, are known as nodular graphite (SG) promoter. There have
been reported many types of nuclei, such as Igarashi et. al [1] found MgO/MgS enveloped by
(Mg,Si,Al)N, nucleating a nodule. Also CaS, MgO and Al2O3 were observed in the core of graphite
nodule while (Al,Mg,Si)N in the shell. FeClx was found together with (Mg,Al,Si)xOx particle in the
core of a graphite nodule in high purity cast iron [2]. Nakae et. al [3] analysed different types of
compounds as nuclei for nodules such as (Mg,Si, Al)N-oxides, (La,Ce,Nd)OxSy, FeClx,
(Ce,La,Nd)S and SiO2 as core compounds, and concluded that the formation mechanism of nodular
graphite is not based on the nuclei . In flake graphite, MnS was heterogeneously nucleated by
different types of oxides which became nucleation site for the flake graphite nucleation [4].
Contrary to the inoculation effect there have been evidences where nodular graphite was
obtained without any inoculation such as Sadocha et. al [5] found only nodular graphite in a
spectroscopic purity ternary alloy (Fe,C,Si). At slightly lower purity level many curved and bent
graphite crystal appeared. According to Gruzleski [6] the morphological change is brought about by
the ability of graphite to grow as curved crystals under certain condition while under other
conditions this ability does not exist and only flakes are formed. According to Double et. al [7] and
Johnsson et. al [8] Mg does not have direct action on graphite spherodization but it rather acts as a
scavenger for those elements which stabilizes the flake form. According to Velichko et. al [9],
vermicular graphite grows initially as spheroids, but later due to sufficient amount of O and S in the
residual melt [10] develops branches with the crystal structure similar to flake graphite. Chang et. al
[11], suggested the presence of Fe-C cluster in the melt which creates different polarity due to
difference of the ionization energies in Fe and C, where C atoms exhibit weak negative polarity, and
Fe weak positive polarity.
Franklin et. al [12] made secondary ion mass spectroscopy (SIMS) analysis on flake and nodular
graphite. Higher oxygen content was found in the flake graphite but sulfur content was much lower
than oxygen. In the nodular and compacted graphite the oxygen and sulfur content was lower
compared to flake graphite. According to Hofmann et. al [13] about of the oxygen content was
present as SiO2, 8 ppm as FeO + MnO, the remaining being bound as silicates, mixed oxides or
All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP, (ID:, Jnkping University, Jonkoping, Sweden-28/11/14,09:18:12)

Materials Science Forum Vols. 790-791


more stable oxides than SiO2 such as Al2O3 or TiO2. Elbel et. al [14] also recorded the oxygen
activity for FG, CG and SG at 1350 C which are 0.97 ppm, 0.30 ppm and 0.16 ppm respectively.
In this investigation, nodular graphite and flake graphite growth morphology was examined in
Field Emission Gun (FEG) SEM after performing ion etching on the samples. The effect of O and S
concentration in the melt on the graphite growth morphology was studied experimentally and
theoretically with the help of thermodynamics.
Experimental procedure
The composition of alloys under investigation is provided in Table 1. Two alloys A1, A2 were
prepared in the laboratory using pure Fe (99.99), C(99.9999) and Si (99.9), in the ceramic coated
crucibles. The composition of these alloys was measured with Spark Emission Spectroscopy (SES).
T640-6 sample was inoculated with Vaxoninoculants (Provided by Jaques Lacaze, CIRIMAT,
ENSIACET, Universit de Toulouse, France). High Frequency (HF) induction furnace was used
with a graphite suscepter, placed between the coil and the crucible, in a protective atmosphere of
high purity Argon. A few de-oxidation experiments were performed by adding pure Mg, Ca and Sr
to the melt and cooling down to room temperature, while using MgO crucibles. The final
composition was not measured after de-oxidation experiments. Samples were examined along the
perpendicular section in the SEM. Experiments A2-4 and A2-5 were performed on the sample
which was treated with Ca (A2-2), in the DSC equipment using zirconia crucible, under argon
atmosphere. Ion etching was performed perpendicular to the surface for 5 min (PECS Gatan:
Beam 10 KeV, Etching gun ~380 A, left and right gun 10 and 5 A) on the sample T640-6 and
A1-1. The morphology of graphite was studied with InLense detector attached to FEG-SEM. CrossSection Ar ion polishing was used on Mg treated sample, parallel to surface while removing 75
micron deep surface.
Table 1. Experiments and experimental

Table 2. Investigated alloys composition.

Sample T640-6 was examined with InLense detector in FEG-SEM, after performing ion etching.
A star like growth of the graphite was observed in the centre of the graphite nodules (Fig.1(a,d)).
The branches were extended outward to some distance from where onward the circumferential
growth mechanism was dominant. Those nodules with star like growth, emerging from the middle
of the graphite, do not seem to have any inclusion in the middle as the one shown in the Fig. 1
(except c). The nodules with an inclusion (nuclei) in the centre had circumferential growth by
following the shape profile of the inclusion. In Fig. 1e, the central part did not have any inclusion,
but the graphite formed in layers as indicated in the magnified image. 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.

Fig. 1: T640-6 sample, quenched at eutectic temperature. InLense detector images

after Ar ion etching using PECS.


Solidification and Gravity VI

De-oxidation of the melt using pure Mg. The microstructure contained combination of nodular,
compacted/vermicular and undercooled fine graphite (Fig. 2a). In Fig. 2c, a bundle of graphite layer
have changed its direction of growth from circumferencial to tangential direction which at certain
distance again have changed the growth morphlogy towards circumferencial growth mechanism,
resulting in two adjacent nodules. Two step growth could be observed in many nodules as shown in
Fig. 2d, where the outer shell around the nodule was formed during the solidification process. The
circumferencial profile of the growing graphite layers exactly followed the shape profile of the
nucleating agent (MgO/S inclusio, Fig. 2d). In Fig. 2(e,f,g,h) after cirtain growth of the graphite, a
transition towards flake like morphology was occurred.

Fig. 2: A1-1 sample, FEG-SEM InLense detector images.

Highlighted black

Fig. 3: A1-1, FEG-SEM images of Cross-Section Ion Polished surface, shows MgS particles.
As shown in Fig. 3, many MgS particles were observed both in the undercooled graphite region
as well as in the nodular graphite region, with and without any connection to graphite. Most of them
were below 1 m in size. A relatively large round MgO particle was found in the austenite region,
sorrounded by large number of nano sized MgO particles (Fig. 3c).
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 (Fig. 4d), with a complete absence of undercooled fine
graphite (Fig. 4). The fraction of graphite in this sample was less due to the formation of CaC2
which can stabilizes or nucleate cementite. Due to multiple nuclei of CaO/S, a compacted like
graphite was produced as indicated with arrows in Fig. 4c. C was often found in the middle of the
noduels as shown in Fig. 4(b). Sample A2-2 when re-melted (A2-4), with low oxygen content
resulted in fine undercooled graphite together with some course graphite flakes (Fig.4e), but with
high oxygen content (A2-5), the microstructure was consist of extremely fine vermicular type of
graphite, with no trace of course flakes (Fig. 4f).

Fig. 4: (a,b,c,d) Ca treated sample A2-2, Ar Ion etched, (e) Re-melted Ca treated samples
A2-4, (f) Re-melted Ca treated samples and 1 wt. % O addition.
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. 5. After ion ethcing there

Materials Science Forum Vols. 790-791


were some particles which contained amorphous graphite surrounded by layers of graphite (about 510 nm thick) as indicated in Fig. 5(d,e), also the inner part of Fig. 5(f,g) seems like amorphous. The
growth mechanism in the other large size irregular graphite was flake like but with many different

Fig. 5: A2-3, InLense detector images of the

Sr treated sample, after Ion etching. White
marked regions in d, e, f and g indicates
By adding different types of elements to liquid melt, one changes the concentration of dissolved
trace elements (O, S, N, P etc.) in the melt by forming different types of inclusions depending on
the affinity of the element with the trace elements. Ellingham diagram (updated by the creators)
[15] is re-drawn (Fig. 6c) to calculate the energy of formation of some important types of reactive
elements. Those elements which have the highest affinity towards oxygen such as Y and Ca might
be consumed mostly prior to solidification starts; however if oxygen reduces to the equilibrium
value with those active elements, the remaining elements can form sulfide particles during
solidification. In the melt, the amount of sulfur is usually higher than oxygen which provides
opportunity for new particles formation. From EDX analysis, only few of the particles were found
MgO, but most of them were MgS. Their smaller sizes depicts that they have nucleated at the end of
solidification. The steeper is the formation energy line, the quicker it will reach the limit of
homogeneous nucleation, as shown for MgS and SrS (Fig. 6(a,b)). Detailed formulations and
calculations have been earlier reported by Muhmond et. al [4] for hypo eutectic iron. By adding
pure Mg, it will form MgO due to its higher affinity towards oxygen, with or without silicates,
which together have served as nuclei for the graphite nodule to grow on it. Primary graphite nodules
formed will float up, causing a change in the remaining liquid composition towards hypo eutectic.
At the inter-dendritic areas, new MgS particles will form (Fig. 6(a,b)), due to enrichment of sulfur
in the melt, since oxygen was already reduced to lower level in the melt prior to solidification. SrS
might be formed as well; however in the presence of Ce, Mg and Ca it is difficult to nucleate SrS
due to its lower affinity to Sr. If the newly sulfide/oxides particles are formed prior to, or at the
beginning of eutectic reaction, they could serve as nuclei for graphite. The morphology of the
graphite growth will depend on the concentration of dissolved trace elements such as O and S
concentration around the growing graphite. The oxide/sulfide particles which nucleates close the
end of solidification, may or may not serve as nuclei for graphite. Many MgS particles were found
connected to flake graphite which proves that the dissolved content of sulfur was above the critical
limit for transition of graphite. The formation of new particles is important because they reduces S
and O concentration, however in the absence of such inclusions, the concentration of the mentioned
dissolved elements would continue to increase and the graphite morphology will be significantly
modified. From some other results often we found very few MgS particles in the undercooled
graphite region compared to the other forms of graphite. An example is shown in Fig. 2b marked
area A, larger graphite particles are round but the smaller ones are under transition towards
compacted graphite but in the marked area B , the graphite are elongated, shows the difference in
composition (S and O) of the melt locally. In the marked area C, a nodule being trapped by the
growing eutectic graphite is found.
The Ca treated sample was completely free from undercooled fine graphite or normal flake
graphite, due to the effective scavenging of oxygen and sulfur from the liquid. A pore that might
have been formed during cooling of melt, was later filled by C diffusion towards it (Fig. 4d).


Solidification and Gravity VI

Increasing oxygen content have changed the graphite morphology drastically from flake graphite
towards extremely fine vermicular type of graphite, in the re-melted Ca treated sample (Fig. 4f).
Due to the presence of about 2 ppm oxygen in the argon gas and melting in the alumina crucible
would have allowed the melt to dissolve some oxygen in it and Ca might have been faded out, thus
causing the formation of undercooled type of graphite. The opposite happened in the Sr treated
sample where due to higher affinity of Sr towards O, it reduced oxygen content in the sample while
sulfur remained less affected which played a role in modifying the growth morphology to normal
flake graphite.
If one carefully observe different types of graphite morphology shown in Fig. 2(a,b) and Fig.
5(a,b), the transition of graphite morphology from the centre of the austenite dendrite towards the
eutectic changes from nodular to compacted/vermicular and then undercooled fine graphite, or even
flake graphite finally. The explanation can be given by the O/S content dissolved in the liquid,
which enriches due to micro-segregation from the edges of the dendrite towards the last solidified
region. By getting closer to the end of solidification, the O/S content increases exponentially. In the
absence of de-oxidizers and de-sulphurizer, it could easily be above the critical limit and thus
causing transition towards either flake graphite or undercooled graphite growth morphology,
depending on the type of trace element and its concentration.

Fig. 6: (a,b) Homogeneous nucleation of new MgS

and SrS particles during solidification, while
assuming hyper eutectic composition, KMg part. = KSr
= 0.031 and start and end temperature = 1200
and 1120 oC. (c) Ellinghams Updated diagram [15]
,Thermodynamic energy of formation of different
oxides and sulfides, (except for SrS [16]).
Concluding remarks
The growth of graphite in a dendritic or star like manner, at the centre of nodules, depicts certain
relationship of the graphite growth morphology with the lattice structure of the graphite and/or 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, is under investigations. MgO and MgS being present in the centre of a nodule
as well as connected to/or close to undercooled/vermicular graphite gives an indication that the
concentration of trace elements around the growing graphite during cooling and solidification could
affect the graphite growth morphology. The possibility of trace elements (O, S etc.) being co-valent
bonded in the graphite lattice, stabilizing either flake or compacted/vermicular growth of graphite,
will be carefully analyzed in future.

Materials Science Forum Vols. 790-791


The authors would like to thank Elkem AS Foundary Technology Products R&D for providing the
financial support.
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Solidification and Gravity VI


Graphite Growth Morphologies in Cast Iron