Technical Information 5

Inoculation Mechanisms
Several theories have been developed in the past to explain the mechanisms of graphite
nucleation during solidification of cast iron. Most theories are based on the assumption
that graphite is formed as a result of heterogeneous nucleation from non-metallic sub-
strates during solidification and that minor elements such as Ca, Ba and Sr play an impor-
tant role in the nucleation process.

Ductile Iron

In magnesium treated cast irons, micro-inclusions after treatment contain mainly magne-
sium, calcium, sulphur, silicon, and oxygen. These are primary reaction products of the
magnesium treatment. The inclusions are composed of a sulphide core and a faceted
outer silicate shell. The sulphide core contains both MgS and CaS, while the outer shell
consists of complex magnesium silicates (e.g. MgSiO3, Mg2SiO4). These phases will not
act as potent nucleation sites for graphite during solidification because of a large
nucleus/graphite interfacial energy barrier.

After inoculation with a Ca-containing ferrosilicon, hexagonal silicate phases of the CaSiO3
and the CaAl2Si2O8 type will form at the surface of the existing sulphide/oxide inclusions
produced during nodularization. These calcium silicates will then act as very favourable
sites for graphite nucleation during solidification, due to their hexagonal crystal structure
that matches the graphite crystal lattice very well (i.e. low energy interface). The figure
below to the left shows a typical micro-inclusion in ductile cast iron that is formed after
nodularization, while the figure to the right gives a schematic representation of the inclu-
sion composition after inoculation with ferrosilicon containing either Ca, Ba or Sr.

Major constituent phases:

XO SiO2 or
XO Al2O3 2SiO2
Shell: MgO SiO2
2MgO 2SiO2

Core: MgS
CaS Where X = Ca, Sr or Ba

Duplex sulphide/oxide micro-inclusion in ductile Schematic representation of an inclusion after

cast iron inoculation with a X-containing ferrosilicon
inoculant (X denotes Ca, Ba or Sr).

The surface shell contains hexagonal calcium silicates formed during inoculant addition,
while the bulk particle is a product of the nodularization treatment. Hence, the inoculation
does not increase the total number of nuclei particles in the melt, but rather modifies the
surface of the already existing products from nodularization.

This explains the important link between magnesium treatment and inoculation, and that
the basis for effective ductile iron inoculation is laid during nodularization. The resulting
nodule number density will also differ greatly due to the inclusion surface modification.

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Technical Information 5 2

When inoculation is carried out with a strontium or barium containing ferrosilicon inoculant,
hexagonal silicates equivalent to the calcium silicates will be formed (i.e. SrSiO3,
SrAl2Si2O8, BaSiO3, BaAl2Si2O8).

Grey Iron

In grey iron the nucleation mechanisms differ somewhat from the situation in ductile iron,
primarily due to the fact that magnesium is not added prior to inoculation. Consequently,
other substrates will play the important role as sites for the Ca, Ba or Sr silicates formed
during inoculation. In principal, the same types of inoculants can be used for both grey
and ductile irons, and the inoculation mechanisms from hexagonal silicate phases at the
surface of primary inclusions are equal for all types of irons.

However, in grey cast iron the lack of primary magnesium sulphides and silicates means
that other particles have to take the primary role. It is assumed that the presence of a high
number of manganese sulphides (MnS) replaces the magnesium containing particles
found in ductile iron. The relation between manganese and sulphur in grey cast iron
should be as follows:

%Mn = 1.7 x %S + 0.3

When this balance is correct, the optimum conditions for the formation of small MnS par-
ticles is obtained. Furthermore, to have a highest possible number density of MnS partic-
les as a basis for effective inoculation, the sulphur content of grey irons should be signifi-
cantly higher than for ductile irons. Normally, a sulphur content between 0.05 and 0.15%
is recommended.

Some Important Considerations

• Pure ferrosilicon has no inoculation effect whatsoever.
• Inoculation does not increase the number of potential nucleation sites in grey and
ductile iron but modifies existing sites to a beneficial form.
• The important consideration in effective inoculation is the formation of a high
number of non-metallic micro-particles (sulphides and oxides) during magnesium
treatment of ductile iron and the formation of numerous manganese sulphide
particles in grey iron.
• Minor elements such as Ca, Ba and Sr as well as silicon in inoculants are critical for
powerful effectiveness of an inoculant material.
• The base metal oxygen content is also critical in the formation of effective oxide
substrates for graphite nucleation.