Technical Paper

Inoculation of cast irons:

practices and developments
Dr John Pearce CEng Prof MICME BSc PhD FIM
National Metal and Materials, National Science
and Tech Development Agency, Ministry of
Science and Technology, Thailand
Introduction
Continuing developments in liquid metal treatment technologies have
made major contributions to the quality, performance and reliability
of metal castings. Advances in melt conditioning, in magnesium
treatments to produce Ductile and Compacted Graphite Irons, and in
inoculation techniques have ensured that Cast Irons remain key and
competitive engineering materials. The combined interactions and
influences of liquid metal treatments and other factors such as alloy
composition, trace elements, section size & design and cooling rate
etc. are covered in standard texts (1-3). The aim of this short review is
to outline the development of inoculants and inoculation practices,
and to also reflect on recent improvements in our understanding and
practical control of graphite nucleation.
In liquid iron preparation the usual sequence of treatments involves:
Initial control of composition and inherent nucleation by melt preconditioning
Mg treatment (when Ductile or Compacted Graphite Irons are
being produced)
Inoculation.
The report begins by looking at the main aspects of inoculation
and the materials used as inoculants, before commenting on how
inoculation can be effectively integrated with the other treatments.

Inoculation: Some key points

Inoculation is the term used to describe the process of increasing the
numbers of nucleating sites from which eutectic graphite can grow
during the solidification of flake, nodular and compacted graphite
irons. The main aim of inoculation is to minimize the degree of
undercooling of liquid iron during eutectic solidification, and hence
to make sure that the resultant cast microstructures are completely
free from eutectic carbides. Inoculation also plays a major part in the
control of eutectic graphite morphology and distribution, and hence
in control of the levels of pearlite and ferrite in matrix structures.
In flake graphite cast irons inoculation refines the eutectic cell size

Fig. 1. Effect of inoculation on eutectic cell size and chill depth in wedge samples
(schematic). (a) before inoculation (b) immediately after inoculation (c) fading due
to holding time after inoculation before pouring(2)

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of the austenite-flake graphite eutectic reducing

the continuity of the weak graphite phase and
thereby increasing tensile strength. Inoculation is
not normally required for higher carbon equivalent
flake irons which are used to produce lower
strength grades but it is a must for the lower
carbon equivalents used for flake iron grades
requiring minimum tensile strengths in the range
of 250 - 400N/mm2.
In flake graphite (grey) irons inoculation is used to:
Prevent eutectic carbides, especially in thin
sections and at corners
Ensure a uniform distribution of fine type A
graphite flakes
Avoid the presence of undercooled graphite
and the associated soft free ferrite in the
matrix.
The formation of eutectic carbide is called chill.
It increases the tendency for fracture of the casting
during handling or service and gives hard spots
that seriously reduce machinability.
Fig. 1 shows schematic views, using wedge
test type samples, of the effects of inoculation
in reducing chill and refining cell size in a
flake graphite iron. Inoculation also avoids the
formation of large eutectic cells consisting of the
very finely branched form of graphite (undercooled
graphite) that can grow at high degrees of
undercooling when nucleation of the melt is low.
Because of its high surface area undercooled
graphite promotes the formation of a ferrite rather
than a pearlite matrix (fig. 2). Free ferrite lowers
strength, hardness and wear resistance. It also
reduces machinability since it encourages the
formation of a built up edge reducing both tool life
and the quality of machined surface finish.
In ductile irons eutectic carbides tend to form
in the intercellular regions throughout the casting
but are more likely to occur in thin sections (due
to high cooling rates as in fig. 3) or heavy sections
(due to segregation of carbide formers). The
intercellular regions, in between the austenitenodule eutectic cells are the last zones to solidify
and will contain elements which segregate into
the liquid: notably manganese, chromium and
other carbide forming residuals such as niobium,
vanadium and titanium. Inoculation must ensure
that sufficient numbers of graphite nodules are
nucleated to prevent the formation of intercellular
carbides, and also to encourage a high degree of
nodularity. At low nodule numbers, the larger the
graphite nodules the greater is the tendency for
reduced nodularity.
Unfortunately the effects of inoculation
treatments are transient and they become reduced
with time when the inoculated metal is held in
the ladle before castings are poured. This is
called fading. As illustrated in fig.1(c), fading in
flake irons leads to a greater tendency to form

FTJ January/February 2008

chill, and to increases in eutectic cell size thus decreasing

tensile strength. The effects of fading of three common
inoculant materials in grey and ductile irons can be seen
in fig. 4. It is seen that for both types of iron the rates of
fading are highest immediately after inoculation. In ductile
iron the reduction in nodule number with time will tend
to promote less ferrite and more pearlite in the matrix.
During the holding of treated metal intended for ductile
iron production the problem of fading is even more serious
since both Mg loss due to volatilisation and inoculant
fade occur. If metal is held too long, without any back up
treatment, this will result in unacceptable castings due to
the presence of sub-nodular graphite.
To reduce the effects of fading castings should be
poured as soon as possible after inoculation treatment
but often in production situations this cannot always be
achieved. The problems of inoculant fade in flake and in
ductile irons, the development of reduced fade inoculants,
and of late treatments via pouring stream or in the mould
techniques have therefore been and continue to be major
areas for R&D, and for treatment technology improvements
(4-7)
.

Technical Paper

Fig. 2. Undercooled graphite formed in grey iron as a result of low melt

nucleation (x1000)

Inoculant materials
Foundries are often confused by the extensive range of
both inoculants and nodularising agents that are available
from the ferroalloy producers. Examples of some typical
compositions are listed in Table 1. Most inoculants are
based on ferrosilicons containing about 70-75% Silicon, or
on ferrosilicon - graphite mixtures. In flake irons the normal
levels of inoculant ladle addition raise the silicon content
by about 0.2%, whereas in ductile irons larger additions
are used, raising Si level by around 0.5%. Inoculant grades
containing around 45-50% Si are also used where pick up of
Si must be limited. Research into understanding the effects
of inoculation, and into the development of more potent
ferrosilicon compositions, has been continuing since the
early 1960s. Important observations from some of this
work (4-10) can be summarised as follows:
The effect of silicon on eutectic graphite nucleation and
chill reduction is much more marked if the silicon is added
as an inoculant than if it were just added to the furnace
charge.
The relationship between graphite nucleation and chill
reduction is not simple one in that inoculants giving the
finest eutectic cells (high cell counts) do not always give
the greatest chill reduction.
For ferrosilicon to be an effective inoculant then it
must contain small amounts of minor elements such
as calcium, aluminium, zirconium, cerium, barium,
manganese and strontium.
Lack of control in the use of inoculants can give rise to
other problems such as shrinkage defects caused by
excessive mould dilation, pinholes due to Al pick up,
and inclusions of undissolved inoculant and slag.
The rates of fading of inoculation treatments are most
rapid during the first few minutes after treatment and
the effects of the treatment are halved after about five
minutes of holding.
Barium containing ferrosilicons tend to be more
persistent and can show a reduced tendency to fade in
ductile irons.
Graphitic carbons with suitable crystal structures can
inoculate flake irons but not ductile irons. Amorphous
carbons do not act as inoculants.
It is difficult to effectively inoculate grey irons with
sulphur contents below 0.05%, especially below 0.03%,
using conventional ferrosilicon inoculants.

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Fig. 3. Presence of eutectic carbides in thin section ductile iron x750

Fig. 4. Fading of inoculation effect on eutectic cell counts in grey iron

and nodule number in ductile iron(5,7)
1. FeSi with Ba and Ca 2. FeSi with Sr and low AI
3. FeSi regular foundry-grade

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Technical Paper
Table 1: Approximate compositions of some typical Ferrosilicon based inoculant materials, in each case the balance is Iron

The FeSi-RE type can also contain small controlled amounts of Oxygen and Sulphur to boost nucleation where high
nodule numbers are needed in producing ferritic ductile iron.
Magnesium ferrosilicons used as nodularising agents normally contain around 45%Si and have a range of Mg levels
from 3 10%, some grades may contain up to 3%Ca, 1%Al, and 3%RE.
Nodularising agents and inoculants are supplied in controlled size ranges to suit their intended modes of application e.g.
3-25mm for MgFeSi, 2-6mm for ladle inoculant, and 0.2-0.6 for late in stream inoculant.

Most commercial ferrosilicon based inoculants

therefore contain up to around 5% of carefully
controlled levels of elements (Ca, Al, Sr, Ba, Mn,
Zr, Ce, etc.) that are capable of forming microinclusions of complex oxides or oxysulphides
having suitable surface and crystallographic
characteristics to heterogeneously nucleate
graphite (11-12).
The problem of inoculation of low S grey irons
has grown as increasing numbers of foundries
have replaced cupolas with electric induction
melting, and in turn are using less pig iron and
greater proportions of steel scrap in charges. For
example, many automotive
iron foundries in Thailand base their charges
on very low S steel scrap from their automotive
pressings neighbours. These foundries do not
want to add S to their grey iron melts (allowing
the use of normal levels of conventional grade
ferrosilicons) since they also produce ductile
irons and do not want to separate foundry
returns. To meet the needs of such foundries
the major inoculant producers have developed
special ferrosilicon inoculants containing Sr and
rare earth (RE) elements such Ce and La that can
be used to treat very low S grey irons at relatively
low addition rates. Likewise an inoculant
containing zirconium has also been developed
to gather nitrogen as zirconium nitrides and so
prevent N related blowhole defects.

Inoculation in the production of ductile

irons
A number of treatment methods have been
devised to introduce magnesium into liquid
irons of suitable composition, with Sulphur
levels preferably below 0.02%, to ensure that the

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graphite phase grows in a nodular form (13-17).

Magnesium is volatile and extremely reactive at
liquid iron treatment temperatures so it is more
conveniently added in the form of a carrier alloy
to avoid the dangers of explosive reaction, to
ensure economic and consistent recovery of
magnesium, and to minimise fume. The first
alloys used were based on Nickel-15% Magnesium
but foundries can now choose from a wide
range of treatment alloys many of which are now
based on Magnesium Ferrosilicons containing
between 3-10% Mg with 50-70%Si (13). Unalloyed
magnesium can be used for safe and efficient
treatment if specially designed treatment
equipment is employed, e.g. converter or
pressurized ladle, cored wire, etc (14-16). Treatment
with pure magnesium is especially suitable for
base irons of higher S content where combined
desulphurisation and nodularising treatment is
needed.
Depending upon the purity of the base iron
small amounts of cerium may be included with
nodularising treatments in order to inhibit the
effects of subversive trace elements such as
antimony, arsenic, lead, tin, etc. If cerium is not
used the presence of such elements can influence
nodule formation and can lead to imperfect
nodular graphite structures resulting in irons
with inferior mechanical properties.
Most ladle treatment methods involve the use
of magnesium ferrosilicon alloys in specially
prepared ladles as in the sandwich and tundish
(covered ladle) processes (16-18). Compared to
open ladle treatments, the use of a covered
tundish ladle gives better Mg recovery with
much less fume and glare (18). Commercial
Mg ferrosilicons typically contain around

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Technical Paper
3-10%Mg, 44-50%Si, with up to 2.5%Ca, and
up to 2.5% RE (Ce, La, etc.). Calcium reduces
reactivity increasing Mg recovery and provides
some inoculation effect. The rare earths (RE)
neutralise deleterious trace elements, assist in
nodularization, and like Ca, reduce reactivity and
provide some inoculation. The lower Mg content
ferrosilicons can be used very effectively, via flow
through reaction chambers, tundish type ladles,
or in the mould treatments, giving high levels of
Mg recovery (due to low reactivity) together with
some inoculation effect.
Regardless of the form of Mg treatment
employed, the treated iron must inoculated
with a suitable inoculant to prevent eutectic
carbides and to encourage a uniform distribution
of well formed graphite nodules throughout
the structure, the amount of inoculant used
depending on the nature of the prior Mg
treatment. For example, treatment with pure Mg
or Ni-Mg type alloys requires the use of larger
inoculant additions for effective nucleation.
As mentioned earlier, treated iron must be
poured into moulds as soon as possible after
treatment so that the effects of both Mg loss
and inoculant fade are minimised. There are
a number of post-ladle or late inoculation
treatment systems that have been developed
to avoid these fading problems. These include
metering measured amounts of controlled size
inoculant from a dispensing unit to the pouring
stream as it enters the mould, and the use of
inoculant containing cored wire in a fed-wire
arrangement, the latter being used particularly
in automatic pouring systems. Cored steel wires
from 5 -13mm in diameter are used to transport
powdered treatment alloy or inoculant into the
iron at the pouring station. Experience in the use
of such systems has shown that they can replace
all or part of the ladle inoculation resulting
in savings in the amount of inoculant used
and reduced Si increments in the iron. These
treatments are consistent and reproducible but it
must be remembered that they can only back up
or replace ladle inoculation if there is sufficient
residual Mg left in the iron. If Mg treatment
has been ineffective (e.g. too high a treatment
temperature giving low recovery) or if too much
Mg has been lost because of delays in pouring
then good nodularity cannot be obtained even if
the degree of nucleation is high.
An alternative approach is to use in the
mould inoculation where the inoculant is placed
in the pouring bush or in a cavity in the runner
system, this latter technique also being used for
Mg treatment. In this case a specially designed
treatment chamber is incorporated into the filling
system to make sure that the treatment alloy (Mg
alloy +inoculant) dissolves uniformly, treating
consistently all the metal that enters the mould.
Ceramic filters are also used in the system such
that only clean, correctly treated metal enters
the casting cavity. Each mould is a separate
treatment and this can present greater inspection
problems than ladle treatment. The in the mould
type treatment is most suitable for long runs
of simple shaped castings where automatic
assessment of nodularity can be easily made.

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Pre-conditioning of cast iron melts

Pre-conditioning involves the treatment of liquid iron before
nodularising and/or inoculation treatments. The aim is to promote
the formation of type A graphite in grey irons and the formation
of nodular graphite in ductile irons by ensuring that melts have
consistent and sufficiently high states of nucleation. Improvements
in our understanding of the roles of Oxygen and Sulphur levels and
associated oxy-sulphide micro-inclusions in graphite nucleation (11,19),
and of the influences of recarburiser characteristics on nucleation
potential (20-22), coupled with developments in interpreting the data
from cooling curves during thermal analysis (20,21,23) have encouraged
foundries to pay much more attention to melt preparation. In
particular work on the use of recarburisers has shown that foundries
can improve the metallurgical condition of melts in terms of control
of Carbon Equivalent and nucleation potential if graphitic carburisers
with high degrees of crystallinity are used in place of amorphous
carbons (22). Pre-conditioning has proved its effectiveness in the
production of ductile irons (20,21,24). For example it is reported (24) that
with pre-conditioning the spread of hardness and % elongation values
were 150-190Hb and 18-24% respectively compared to values of
160-240Hb and 10-24% without pre-conditioning. Also in producing
ferritic ductile irons pre-conditioning with very small additions of
Cerium (20-60ppm) and Bismuth (10-20ppm) has been recommended
to ensure sufficiently high nodule numbers.
With the increasing interest in reducing wall thicknesses in iron
castings and in producing Compacted Graphite Irons (CGI) without
the use of Ti, pre-conditioning of melts, computer aided thermal
analysis, and improved Mg and inoculation treatments will remain the
key areas for future developments. For example, attention has been
drawn to the care needed in inoculating CGI (25) where inoculation
must prevent eutectic carbides without promoting the formation
of graphite nodules. This work has also shown that with correct
pre-conditioning, if a suitable inoculant material is used in place of
steel as the cover in sandwich ladle treatment, then it is possible to
produce satisfactory CGI structures without any post-inoculation. It
has also been found that CGI can be successfully produced without Ti
by using fed wire treatment with Ce bearing MgFeSi (26).
In spite of many advances in the understanding and technology
of inoculation treatments, some foundries still do not pay sufficient
attention to the correct use of inoculants. For example, putting the
inoculant at the bottom of a slag covered ladle (instead of adding it
to the pouring stream during filling of a clean properly maintained
ladle) and then wondering why there are problems with carbides and
inclusions. The dos and donts of inoculation practice are well
documented (e.g. 27). Foundries with inoculation problems should revisit
these and also seek the detailed technical advice readily available
from the major ferroalloy and inoculant suppliers to make sure that
they are using the best inoculant for the job, and using it in the
correct way.

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Technical Paper
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