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Tugas Paper: Graphite Formation in Nodular Cast Iron

Reasons for the formation of nodular graphite have given rise to numerous hypotheses and
speculation over the past 30 years, with various well-known authors conducting surveys.
1965. A review of the formation of spheroidal graphite in cast iron. S.Banerjee [quot.2,3],[7]
The literature has been critically examined by listing about 150 experimentally observed facts
which are pertinent to the formation of spheroidal graphite. The discussion seems to indicate
that the nucleation of a spheroid takes place necessarily in the liquid state even in a Mg-treated
cast iron, and its growth takes place by the diffusion of carbon atoms from the source (which
could be the melt, austenite or decomposition of cementite) to the spheroid nucleus. This idea
is consistent with all the listed observations.
For the earlier research there has been found that the addition of Mg or Ca can :
(1) The use of magnesium as a spheroidizing agent produces spheroidal graphite cast
iron having microscopic nodular graphite grains. These nodules have a minimum
effect on the mechanical properties of the cast iron. The mechanical properties are
mainly determined by the type of matrix structure and this imparts the favorable
physical properties of cast iron (low melting point, good fluidity and castability),
with the engineering advantages of steel (high strength, toughness, ductility, hot
workability and hardenability).
(2) The use of calcium as a spheroidizing agent produces grey flake cast iron. The
mechanical properties of the cast iron produced ar influenced by the graphite flakes.
(3) The use of a combined addition of 60% Mg and 40% Ca as spheroidizing agent in
an inmould addition technique produces spheroidal graphite cast iron. This
combined addition reduces the amount of Mg alloy used in the spheroidization
process thereby reducing cost of production. The small shape of the nodule
produced as shown in plate 4 also increases the nodularity of the cast iron.
(4) The use of other varying combined addition produces graphite flakes in the cast iron
microstructure.
As soon as the possibilities and advantages of the "new" material were recognized,
developments followed swiftly with cerium being introduced as a nodularizing element by
Morrogh and NiMg proposed by the International Nickel Company. While reliable production
of cast iron with nodular graphite appeared to be within the reach of every well-equipped
foundry, little was, however, known about the mechanism behind the actual nodule formation.
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Some theories were developed in the early fifties based on experience gained during the
production of the new material but also strongly influenced by the existing ideas about the
mechanisms of graphite formation in gray iron.

1.1 Cementite-theory.
In the early years, heat-treatment was essential to obtaining a nodular structure that was fully
free of cementite. It is, therefore, not surprising that one of the first theories was based on the
view that nodules were formed by the actual decomposition of cementite. This theory had, after
all, been in existence for more than 40 years with regard to the formation of flake graphite in
cast iron. Such thoughts prevailed even after a nodular structure was produced directly in the
as-cast condition. According to Morrogh , one of the pioneers in this field, a graphite nodule
was never formed in the melt, but always by the decomposition of cementite . Dunphy and
Pellini stated that nodules are formed in the neighborhood of existing dendrites, immediately
before the start of the eutectic reaction. Local regions of supersaturated melt are formed close
to the dendrite-arms and it is in these local liquid regions that the nodules form. Further growth
of the nodules takes place by the decomposition of the cementite, build up around the nodule.

Figure 1, nodule formation acc.to Dunphy.

1.2 The Austenite-theory.
De Sy observed that dendrites, found in shrinkage cavities, showed almost the same chemical
composition as the base-material . For this and many other reasons, he believed that nodular
iron solidified without eutectic, but in a mixed crystal system, the latter being formed by
supersaturated austenite. Precipitation of graphite particles, therefore, occurred within the
austenite dendrites with further growth taking place by a peritectic transformation or reaction.
Formation of nodules within a supersaturated austenite crystal according to De Sy is shown in
fig.5.
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Fig.2 Graphite nodules formed by decomposition of super-saturated austeniteFigure 5, nodule

formation within (super)saturated austenite.

Figure 3, nodule formation within (super)saturated austenite acc. to Wittmoser.

1.3 The Melt-theory.
Scheil is convinced that nodules form in the melt, independent of existing austenite dendrites
. The nucleation and initial growth takes place in the melt and upon reaching a certain
dimension tey are encased in a shell of austenite. Further growth takes place by diffusion of
carbon from the melt, via the austenite shell to the existing nodules.
If an austenite encased nodule collides with an austenite dendrite, both structures melt together
to form a new structure in which the original shell and dendrite cannot be detected. Fig. 7.
shows nodule formation according to Scheil as explained by Wlodawer.

Fig.4 Graphite nodules form directly in the meltFigure 7 nodule formation acc. to Scheil.
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Fig.5 Graphite nodules form directly in the melt at dendrite armsFigure 8 preferred nucleation
sites for graphite nodules between austenite dendrite arms (Patterson).
1.4 The Bubble Theory.
In the early days many experiments, using a variety of alloying elements, were conducted in
order to obtain a spheroidal graphite precipitation. The only similarity between these alloying
additions was the fact that they all could be converted into a gaseous form by the molten iron.
This fact lead to the development of the so-called Bubble-Hypothesis, first proposed by
v.Nieuwland , but better publicized by Karsay . The Bubble Theory expounds that the tiny
bubbles in the liquid metal, created by the gas evolution, are ideal sites for nuclei which will
give rise to the growth of graphite nodules. In this theory, the graphite grows radially from the
outside into the bubble as is indicated in fig.5.

Fig.6 Graphite nodules form within gasbubblesFigure 9 Gasbubbles as a template for

the final graphite shape.
1.5 Graphite-morphology.
Other researchers disregarded the question of when and where nodules form, but looked instead
for the reason why graphite separates in a spheroidal shape. Marincek for instance, supposed
that high surface tension was responsible for the ball shape , fig.6. Hillert en Lindblom , on the
other hand, assumed that the crystal growth of the graphite was influenced by the presence of
disturbing atoms , derived from the nodularising elements, in the crystal structure.
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Fig7 Nodule shape is caused by high surface tensionFigure 6 The typical ball-shape is
caused by high surface tension acc. to Marincek.

Once it was generally accepted that nodules formed directly in the melt, other structural
components, such as dendrites, were no longer needed for nodule formation. Soon, they were
to disappear from all theories. Scheil , for example remarks: "To keep it simple, we will speak
about an austenite region, although it actually is an austenite dendrite." . And: "Dendrites are
deformed by the nodules, in such a way that they cannot be recognized afterwards.".

Dendrites also gradually disappear from drawings, as can be noted in Morrogh's schematic of
different stages in the solidification of nodular iron, as can be seen in the following figures:

Fig.8. Successive stages in the solidification of nodular cast iron. Primary dendrites
are left out. Morrogh,1961

Fig.9. The solidification of nodular iron (schematic). Henke,1967

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Fig.10. Various stages of the eutectic in nodular cast iron. Jolley,Holdsworth,1971.

Fig.11. The solidification of the graphite-austenite eutectic in nodular cast iron.

Marincek,1980,.

Refrences :
[1]. http://www.ceesvandevelde.eu/partone.htm
[2]. http://www.metallurgvanadium.com/magnesiumpage.html
[3]. Dawson,S ; “The Effect of Metallurgical Variables on the Machinability of
Compacted Graphite Iron”, 2001
[4]. Oluwole, “Effect of Magnesium and Calcium as Spheroidizers on the Graphite
Morphology in Ductile Cast Iron”,2007