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A Hypothesis for Cast Iron Microstructures

Article in Metallurgical and Materials Transactions B December 2009
DOI: 10.1007/s11663-009-9289-0

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A Hypothesis for Cast Iron Microstructures

JOHN CAMPBELL
The various microstructures of cast irons are reviewed, including carbidic and graphite forms
(ake, compacted, spheroidal, and undercooled, etc.), exploring whether the presence of
externally introduced defects in the form of oxide double lms (bilms) in suspension in melts
seem to provide, for the rst time, a uniform explanation for all the structures and their
properties. Silica-rich oxide bilms provide the substrates on which oxysulde particles form,
nucleating graphite. The presence of the lm provides the favored substrate over which graphite
grows, which leads to the development of ake graphite. The addition of limited Mg to form
compacted graphite destroys all but a remnant of the silica-rich bilms. The oxide lm remnant
is stabilized by the presence of the graphite nucleus, which causes the graphite to grow unidirectionally in a lamentary form. The addition of excess Mg destroys all traces of the oxide
bilms, leaving only the original nuclei, around which graphite is now free to entirely enclose,
initiating the spherical growth mode. Undercooled graphite is the true coupled growth form,
nucleated at even lower temperatures in the absence of favorable lm substrates in suspension;
the graphite adopts a continuous growth mode in a matrix of austenite. Carbides in mottled and
white irons form on the oxide bilms that often lie along grain and interdendritic boundaries,
which explains the apparent brittleness of these strong, hard phases. In most cases of nonspheroidal growth modes (ake and misshaped spheroids), it is proposed that the impairment of
the mechanical properties of irons is not strongly determined by graphite morphology but by the
presence of oxide bilms. Spheroidal graphite iron has the potential for high properties because
of the absence of bilms.
DOI: 10.1007/s11663-009-9289-0
The Minerals, Metals & Materials Society and ASM International 2009

I.

INTRODUCTION

THE forms of graphite in cast irons have been the

subject of intense interest and huge research eorts mainly
since the 1950s, but a full understanding has been elusive.
Readers are referred to the review by Loper[1] for a wideranging synopsis covering many details not included in
this study. Here, a dierent review is made of the
literature, exploring the possibility of a unifying approach
based on the hypothesis that oxide lms (as doubled-over
bilms) are present in liquid irons.
Recently, a comprehensive understanding of the
microstructure of Al-Si alloys has been proposed in
terms of bilms, explaining both the mechanism of
modication and the structures of hypoeutectic and
hypereutectic alloys.[2] Bilms (double lms), usually
oxides, are introduced into molten metals at every pour
or stirring event. These surface lms, which are doubled
up during the process of entrainment into the bulk, seem
to be of major signicance for the development of
solidication structure.[3,4] Their outer surfaces seem to

be favored substrates for the precipitation of many, if

not all, second phases during solidication, whereas the
inner unbonded interface acts as a crack. The lms are
generally so thin they are eectively invisible to casual
observation, which leads to a liquid that is invisibly
cracked and, on solidication, to a solid whose cracks
may or may not be visible.
Nakae and Shin,[5] among many others, have drawn
attention to the analogous features of Al-Si and Fe-C
alloys. This article is an extension of the bilm hypothesis, which is apparently valuable to an understanding of
the Al-Si system as well as to a possible understanding
of the various morphologies of carbon in the form of
graphite and carbides in the Fe-C alloy system. Naturally, the presence of invisible defects in opaque liquids
is not easily conrmed directly, although it will not be
impossible in the longer term. In the meantime, this
article surveys the experimental evidence from the
literature to ascertain whether indirect evidence is
supportive of this hypothesis.

II.
JOHN CAMPBELL, Emeritus Professor, is with the Department of
Materials and Metallurgy, University of Birmingham, Edgbaston,
Birmingham B15 2TT, UK. Contact e-mail: jc@campbelltech.co.uk.
This article is based on a presentation given in the 3rd Shape
Casting Symposium, which occurred during the TMS Spring Meeting
in San Francisco, CA, February 1519, 2009, under the auspices of
TMS, the TMS Light Metals Division, the TMS Solidication
Committee, and the TMS Aluminum Processing Committee.
Article published online September 1, 2009.
786VOLUME 40B, DECEMBER 2009

THE EVIDENCE FOR OXIDE BIFILMS

IN CAST IRON

De Sy[6] has shown that liquid cast iron generally

contains signicant quantities of oxygen in solution in
excess of its solubility. He concluded, on the basis of
careful and rigorous experiments, that the undissolved
fraction of oxygen was present as SiO2 particles.
Interestingly, by heating to 1550 C, he conrmed the
METALLURGICAL AND MATERIALS TRANSACTIONS B

expectation that the SiO2 solids dissolved because they

became less stable than CO but reappeared on cooling
once again. Hartman and Stets[7] report not only the
presence of SiO2 in suspension but also olivine,
2(Mg,Fe)OSiO2 is found in those irons that contain
Mg. Homan and Wolf[8] nd a variety of oxides,
including SiO2, FeO, and MnO among others, but
superheating and holding at high temperature eliminated many of these. In an elegant study of the
thermodynamics, Mampaey and Beghyn[9] show how
mainly SiO2, together with some FeO, forms in a typical
melt when cooling from 1480 C to 1350 C.
It seems reasonable to speculate that these oxides
almost certainly would not be compact spheres, cubes,
rods, etc. but would most likely be in the form of lms.
Only lms would have a suciently low Stokes velocity
(one or two orders of magnitude lower than particles as
a result of their greatly increased drag) to remain in
suspension for long periods of time associated with these
experiments, as well as the long periods during which
irons are held molten in holding furnaces.
In any case, of course, the lm morphology is to be
expected. During melting in the cupola as droplets of
iron rained down, the natural enfolding of the surface
lm of SiO2 of each droplet would ensure a natural
population of SiO2-rich bilms. Additional treatments
or handling, such as pouring actions, stirring in induction furnaces, and the oxide introduced from the surface
of the charge (whether steel, pig, or foundry returns),
would increase this already large, natural population.
Even so, it is well known that iron from electric furnaces
is more liable to chill formation problems in thin
sections than cupola iron, and this eect has been widely
accepted as the loss of nuclei (in agreement with
proposals made in this article), especially during an
extended time in holding furnaces or pouring systems.
Silica-rich oxides in irons are not stable in some
conditions. For instance, they will be expected to go into
solution if the melt is held above approximately 1450 C
for any length of time.[9] Also, they are rapidly reduced
to Si metal, and their oxygen is removed as MgO when
Mg is added to the melt. A dierent population of oxide
bilms denitely exists in ductile irons that have been
cast turbulently. In this case, the presence of Mg
stabilizes the magnesia, MgO, in the surface lm,
although Si might also contribute, thus forming a
magnesium silicate MgOSiO2, which is equivalent to
MgSiO3. Both magnesium oxide and magnesium silicate
are extremely stable and represent permanent damage
folded into the liquid metal and subsequently transferred to the casting. Although the bilms are known to
have an initially compact morphology as a result of the
turbulence during their formation and are relatively
harmless as cracks, the subsequent straightening of these
bilms by various natural processes, such as the growth
of dendrites, which creates extensive planar cracks, is
common; this process results in extraordinary structures
(Figures 1 and 2)[10] and the phenomenon of brittleness
in so-called ductile iron in the form of plate fracture, as
discussed earlier by the author.[3]
Thus, at least two dierent populations of oxide
bilms seem to exist in suspension in liquid iron, which
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 1A so-called ductile iron casting illustrating brittle fracture as

a result of dendrite-straightened bilms.[10]

Fig. 2Optical micrograph through the fracture surface of platefractured ductile iron shows misshapen graphite nodules growing
on bilms straightened by dendrite growth.[10]

include the following: (1) the hypothesized silica-rich

bilms as a natural population in equilibrium with the
melt, the amount of silica-rich phase being predictable
by thermodynamics, and (2) the known magnesia-rich
bilms in ductile irons are the result of mechanical
accidents that involve the turbulent entrainment of the
VOLUME 40B, DECEMBER 2009787

surface lm into the bulk liquid, which results in

nonreversible damage.
In passing, it is worth drawing attention to the
possibility that other nonoxide bilms are to be expected
in cast irons. For instance, nitride bilms probably form
in cast irons giving rise to the nitrogen ssure defects
associated in the past with high nitrogen binders.[3] Also,
of course, carbon bilms exist in irons in those cases in
which hydrocarbon gases from the mold disassociate on
the hot surface of the melt, so that if surface turbulence
occurs, the resulting carbon lm can be folded in. Such
lustrous carbon defects are not necessarily permanent
because the carbon can slowly dissolve, which explains
why such features are observed in only relatively thin
section castings but not in thicker sections.[3] In this
review of the microstructures of cast irons, only oxide
bilms seem to have signicant roles.

III.

nucleate graphite. Only those shells with low Mn/S ratio

seem to act as nuclei. The mechanisms proposed by
Riposan[16,17] are highly convincing and are in agreement with the general consensus that few nuclei exist
prior to inoculation but are enhanced in eectiveness
and number by preconditioning and inoculation, and
their nal composition consists of mixed oxides and
suldes. Many authors have reported the benecial
eects of S, for instance Chisamera et al.[18]
In this article, the mechanisms proposed to explain
the various morphologies of graphite are based on the
possibility of nucleating particles (probably based on
oxysuldes as described by Riposan[16,17]) eective for
all types of graphite, but the subsequent growth of the
graphite is aected by the presence or absence of oxide
bilms of dierent types. This approach is the rst to
suggest separate functions of the graphite nucleating
particles and graphite growth substrates.

GRAPHITE NUCLEI

Mizoguchi et al.[11] have demonstrated that austenite

is ineective in nucleating graphite. In fact, they nd
that undercoolings below the liquidus of between 200 C
and 400 C are required to trigger nucleation by
austenite. A more unfavorable nucleus would be dicult
to imagine. The question therefore arises, What does
nucleate graphite? This question is all the more intriguing following the work by Mampaey and Xu,[12] in
which they found that a single population of nuclei
could explain both gray and ductile irons.
There is a growing consensus that both ake and
spheroidal graphite nucleate on similar, if not identical,
nuclei (for instance, Warrick[13]) composed of particles
of complex oxides and suldes. This was the conclusion
reached in the rst study after the development in the
U.K. of the microprobe analyzer in 1974.[14] Many
conrmations of this nding have since been made (for
instance Skaland[15]), which suggests that the oxysulde
mix of the various elements will have a spectrum of
lattice spacings ensuring that at least part of the
compound will match graphite, and therefore possibly
constitute a favored substrate. As an example of an
excellent recent study, while working on preconditioning
treatments for gray irons (treatments involving small
additions of elements such as Al prior to inoculation possibly to enhance the population of naturally occurring nuclei in uninoculated irons), Riposan[16,17] denes
a three-stage model for the nucleation of graphite:
(a) Small oxides (<2 lm diameter) are formed in the
melt (from the preconditioner, usually containing Al
and/or Zr, leading to the oxides consisting mainly of
alumina or zirconia).
(b) Complex suldes (<5 lm diameter) nucleate on the
oxides (mainly based on MnS with low Mn/S ratio
but complicated by additions, particularly Ca, Sr,
and Ba). The complex suldes form a shell around
the central oxide.
(c) Graphite nucleates on parts of the sulde shell.
Riposan[16,17] nds that MnS shells with Mn/S high
ratios are numerous in the matrix but do not seem to
788VOLUME 40B, DECEMBER 2009

IV.

FLAKE GRAPHITE IRON (FGI)

AND INOCULATION

Uninoculated iron is characterized by poor control of

the graphite morphology. Flakes occur but are relatively
few in number and uncontrolled in size. The relatively
few opportunities for the carbon to precipitate lead to
relatively large regions of the iron elsewhere being
supersaturated with carbon. Thus, carbide precipitation
is likely in places. The mechanical properties of the iron
are generally poor. In general, as will become clear
during the progress of this account, it seems that some
nuclei exist prior to inoculation, but their number and
eectiveness cannot be relied on. The gradual introduction of the inoculation process occurred from about
1920 onward, and its development continues to the
present day (for instance Skaland[15] and Hartung
et al.[19]). The inoculation process was found to increase
greatly the number of nuclei available, giving a copious
crop of graphite akes of good uniformity of size, with a
reduced tendency to carbide formation and a consequent benet to the mechanical properties and machinability of the iron.
The inoculation process is often carried out by
addition to the melt of granules of a graphite promoter
such as a ferrosilicon, which contains perhaps 50 to
75 wt pct Si. Interestingly, the melting point of such an
inoculant is close to 1210 C, which is below liquid iron
casting temperatures, usually in the range 1350 C to
1400 C. Thus, the added particles melt. However, the
particles take time to melt and time to disperse, forming
temporary supersaturated regions of liquid rich in
silicon surrounding the melting and dissolving inoculant
particles. Hurum[20,21] was the rst to draw attention to
this phenomenon, but it has been studied by several
others since (for instance Fredriksson[22]). Harding
et al.[23] show how this region is eectively undercooled
by several hundred degrees Celsius as a result of its
constitution of nearly undiluted graphite promoter, thus
providing a region in which a high driving force exists
for the nucleation of graphite. Inoculation with graphite
or SiC, and so on, acts similarly to promote regions of
METALLURGICAL AND MATERIALS TRANSACTIONS B

high-constitutional undercooling, which encourages

graphite nucleation and growth on any suitable available substrates that happen to be in this region. The
overwhelming driving force explains the wide variation
of successful nuclei, which, in other circumstances,
would be expected to be of only mediocre, if any,
eectiveness.
Because of the additional trace alloying elements in
the inoculant (particularly group IIA elements of the
periodic table, including Mg, Ca, Sr, and Ba), the MnS
shells around the oxide centers are modied in these
regions in which the additions are concentrated (prior to
their dissipation and dilution in the melt). All this is
taking place in the region highly constitutionally undercooled with respect to graphite, thus naturally providing
the driving force for nucleation of graphite in precisely
the location needed for maximum eectiveness.
Bearing in mind that many (if not all) second phases
precipitate on bilms as preferred substrates,[4] it seems
reasonable to assume that these new graphite nuclei
would also preferentially nucleate on bilm substrates.
Thus, graphite would, in turn, nucleate from those
nuclei already sitting on the oxide bilms. Figure 3
schematically shows a graphite nucleus formed on an
oxide bilm approaching an undercooled region provided by a dissolving inoculant particle. On entering this
region, the nucleus experiences a massive driving force
as a result of hundreds of degrees of eective undercooling, which forces graphite to form around the nucleus.
Harding et al.[23] point out that once nucleated in the
regions of high driving force for initiation, the graphite
particles attached to their nuclei now will emerge from
these regions into the general melt where they will
become unstable and start to redissolve. The observations by Loper and Heine[24] conrm that graphite can
nucleate in both hypoeutectic and hypereutectic irons at
1400 C, well into the liquid range, high above the
expected liquidus temperatures. Mampaey[25] conrms
that graphite forms in the melt prior to the appearance
of austenite. (These observations are contrary to expectations based on the equilibrium diagram based, of
course, not only on equilibrium behavior but also on the
behavior of alloys of perfectly uniform composition,
neither of which applies during the mechanism of
inoculation of cast irons.)

Fig. 3The mechanism of inoculation: (a) a bilm in suspension in

the melt together with nuclei already attached from trace contaminants or preconditioners; and (b) the bilm oating into a region of
high constitutional undercooling surrounding a dissolving inoculant
particle, initiating a graphite ake.
METALLURGICAL AND MATERIALS TRANSACTIONS B

Given sucient time, all the inoculant particles will

have melted and dispersed, leaving no pockets of
undercooling, and all the embryonic particles of
graphite nucleated in the undercooled regions will have
re-dissolved. This is almost certainly the phenomenon
known to all foundry personnel as fade of the
inoculation eect. However, graphite embryos on their
nucleating particles will take time to go into solution,
so that if the melt is cast without undue delay, many
will survive to reach the regime close to the freezing
temperature where they will now start to regrow, as
observed experimentally by Loper and Heine.[24] Feest
et al.[26] nd that although the Si-rich inoculant particles disperse relatively rapidly, the graphite formed
rapidly in these regions is slow to redissolve. This is
reasonable because the graphite initially grows quickly
in the highly constitutionally undercooled region, but it
will subsequently dissolve in the open melt rather
slowly because the graphite will nd itself only modestly above its equilibrium eutectic temperature, so that
the matrix would be eectively nearly saturated in
carbon.
The newly forming graphite cannot grow completely
around the nucleating particle because the particle itself
has itself grown on the planar bilm substrate so that at
least one of its faces is inaccessible (Figure 4(c)) (work
by Riposan[16,17] indicates that only parts of the nucleant
particles are active nucleation sites, so that initial growth
is rather irregular). The silica-rich bilm will form a
next best substrate for graphite, so although insuciently favored to cause nucleation, it is suciently
favored to support the subsequent growth of the
graphite. Thus, in gray irons, the graphite extends
across the bilm, leading to the fairly at morphology of
akes in gray iron. The akes grow in regions ahead of
the solidication front (i.e., above the general eutectic
freezing temperatures) because of the energetically
favored growth of graphite on the oxide substrates in
suspension (Figure 5).[27]
The growth morphology of graphite, extending in
the directions in its basal plane, would favor the
straightening of the bilm (Figure 3(d)). The bilm
would be expected to be extremely thin, possibly
measure in nanometers, its minimal rigidity exerting
negligible constraint of the advancing graphite crystal.
The freedom from restraint would explain the development of relatively perfect crystals of graphite as
observed growing ahead of the coupled eutectic graphite (Figure 5).

Fig. 4(a) A bilm with precipitated nucleus from natural contaminants or preconditioners; (b) additional nuclei provided by inoculant;
(c) graphite nucleation on nuclei in regions of high eective carbon
supersaturation as in Figure 3(b); (d) growth of graphite akes along
the length of the bilm, straightening the bilm, with a consequent
central planar crack in the graphite ake.

VOLUME 40B, DECEMBER 2009789

Fig. 5Extrinsic initiation of straight graphite akes in the liquid,

ahead of coupled growth of eutectic graphite and austenite.[27]

Fig. 6Two populations of akes: extrinsically formed on bilms

and intrinsically grown as a coupled (undercooled) eutectic.[29]

The mechanism proposed above explains the growth

of ake graphite from nucleating particles introduced by
inoculation. Particles that seem to be nuclei for the
initiation of akes have often been observed, and these
particles seem likely to be a universal phenomenon in
both ake and nodular irons.[16,17,28]
Eventually, the advancing solidication front will
overtake those akes growing on bilms oating freely
in suspension in the liquid. Thus eventually, these freely
oating akes will become incorporated into the solid
(Figure 5). Thus, it would be expected to be common to
see gray irons with two separate populations of akes:
(1) those formed by free growth in the liquid (primary
akes) and (2) those formed by coupled growth at lower
temperatures (eutectic akes). The coupled growth
mode is discussed below. A bimodal distribution of
graphite akes is therefore to be expected in most gray
iron microstructures, and it is clearly observed in
Figure 6.[29]
Less obvious but important bimodal distributions are
almost certainly common, as may be inferred from the
790VOLUME 40B, DECEMBER 2009

work of Enright et al.[30] On the rst occasion that these

authors used the highly sensitive fractal analysis technique to assess microstructures of cast irons, they
observed this result. Thus, unless this is an extraordinary coincidence, the populations of primary and
eutectic akes should be expected to be mixed in most,
if not all, ake graphite irons, even though, of course,
such mixtures may not always be obvious to casual
observation.
In agreement with the mechanism described in this
article, Goodrich[31] attributes the Type C iron (ASTM
A247), which is characterized by large, straight akes,
with some branching, to the result of the growth of the
akes in the liquid, unencumbered by the presence of
austenite. Primary akes seems to be a good name for
these forms. He calls these proeutectic akes. They
originate in suspension in the melt and therefore can
oat to the upper regions of a casting. The more
common Type A graphite akes are similar, displaying
only minimal irregularity, suggesting a similar origin
and behavior in the melt. Loper and Fang[32] use deep
etching to reveal what they call pre-eutectic akes, which
exhibit elegant hexagonal symmetry and are apparently
largely free from defects. For many other irons, the
presence of a dense mesh of austenite dendrites constrains the size and shapes of akes and prevents any
signicant buoyancy eects.[1]
More usually in castings, the graphite akes are seen
to branch relatively frequently. In terms of the bilm
substrate, this is straightforwardly understood from the
irregular structure of the bilms. During their entrainment from the liquid surface into the bulk melt, they
tend not to entrain as nicely parallel double lms, but
instead they entrain as randomly folded, messy structures. Thus, folds leading to parts of the double lm at
irregular angles to the main bilm fold are to be
expected and would account for the branching of
growing akes.
Experience of variable performance is also to be
expected. For instance, on the Monday morning after
the melt has been held for the weekend, operators
commonly nd the iron has poor graphite structure,
particularly if the iron has been held in an acid-lined
induction furnace. Riposan[16,17] shows that this is at
least partly the result of the gradual loss of the graphite
nuclei. Part of the eect would also be expected to be
loss of bilm substrates. Similarly, iron heated to high
temperature suers a similar degradation of graphite
structure, almost certainly as a result of the dissolution
of the bilms because of the instability of SiO2 above
approximately 1450 C in the presence of carbon. It
would be interesting to know whether the melt, after
losing its silica-rich bilms at high temperature, would
regain its good solidied structure when cooled once
again, because although de Sy[6] reports that the silica
reappears in the melt on cooling, without some kind of
surface turbulence, the form of the silica may not be a
bilm, nor even a lm, but it may be a compact particle.
As such, it is not likely to be a good substrate for the
development of a good ake structure. Even so, the nal
pouring of the melt into the mold may provide sucient
turbulence to address this problem, which makes the
METALLURGICAL AND MATERIALS TRANSACTIONS B

problem essentially invisible to those attempting to

study the eect.
In agreement with the prediction that graphite grows
on oxide bilms, the eect of oxygen addition to the
melt during the pouring of iron into the mold is
demonstrated by several authors. For instance,
Basdogan et al.[33] and Chisamera et al.[18] found
oxygen to be highly eective in converting carbidic
irons into beautifully inoculated ake graphite irons.
Liu and Loper[34] found that oxygen was necessary to
nucleate kish graphite on the surface of gray iron melts.
Larger quantities of kish were formed at temperatures
below 1400 C, below which SiO2 is stable, and kish was
not observed in Si-free melts. Moreover, Johnson and
Smart[35] describe a critical experiment in which they use
sophisticated Auger analysis to prove that two or three
atomic layers of oxygen (and interestingly, sulfur) are
present on fracture surfaces of gray irons that were
adjacent to a graphite ake (fractured and observed in
high vacuum). In contrast, the hollows in the fracture
surfaces of spheroidal graphite matrix that had contained spheroids exhibit no oxygen. This behavior is
exactly predicted by a bilm hypothesis: If ake graphite
formed on one side of the oxide bilms, then the fracture
surface would necessarily reveal the oxide, but oxides
would be absent in the case of spheroidal graphite iron
(as discussed below). For most intermetallics precipitating on one side of a bilm, the halves of the bilm
appear on both fracture surfaces. However, gray iron
has a curious behavior in that nothing seems to attach to
the graphite, so that both halves of the bilm seem to
have attached to the matrix. It is right to question,
therefore, what role has the bilm played in the fracture
because its central unbonded interface has not seemed to
act as the decohering surface on this occasion. In fact, it
seems likely that the bilm will have nucleated the
decoherence, but the continuing decohering action
seems to follow the graphite interface. This nonattachment (perhaps we should say active detaching)
phenomenon between graphite and other phases is
observed elsewhere in bubble trails in gray irons as well
as in lustrous carbon lms detached from the matrix and
adhered to the sand mold.[36]
Although all the above discussion relates to silicabased bilms, evidence indicates that alumina-based, or
possibly Al-containing Si-based bilms (for instance,
based on mullite or other stable alumino-silicate compound) exist. Carlberg and Fredriksson[37] nd that cast
irons based on Fe-C-Si exhibit ne graphite structures,
whereas those based mainly on Fe-C-Al display coarse
graphite akes. Chisamera et al.[18] conrms that conventional gray irons that contain Al develop coarse
graphite akes. It would be reasonable to expect that
silica-rich and alumina-rich bilms would have dierent mechanical and chemical characteristics and, therefore, would develop dierent qualities of precipitated
graphite.
The relatively poor mechanical properties of gray iron
seems likely to be more to do with the presence of bilm
cracks down the centers of graphite akes (or the sides
of graphite akes if graphite grows on only one side of
the bilm the impression now is that the ake has
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 7Graphite ake exhibiting a central crack (the solid state precipitation of surrounding temper graphite is also fractured o).[38]

decohered from the matrix) rather than any intrinsic

weakness of the graphite itself. It seems possible that
graphite is strong in tension perpendicular to its basal
plane, because although the interplane bonding is not
strong, which leads to the familiar easy shear in its free
condition, there are approximately 1015 bonds per mole
in the graphite surface. The huge number of bonds will
ensure high strength in tension in a situation in which
the graphite is encapsulated, preventing easy failure by
peeling or shear. A crack down the center of a ake is
observed in Figure 7.[38]
In their studies of crack initiation and propagation in
irons, Voigt and Holmgren[39] report many centerline
cracks in graphite akes plus some decoherence from the
matrix.
The above discussion relates to those graphite akes
growing freely in the melt giving rise to large, randomly
oriented akes which tend to oat or settle irregularly,
creating what has been called in the past an anomalous eutectic.

V. COUPLED EUTECTIC GROWTH

OF GRAPHITE AND AUSTENITE
In this section, we move the focus from anomalous
to the truly regular, classic eutectic form, in which
austenite and graphite grow in a coupled mode.
In the absence of suitable nuclei that have formed on
oxide substrates in suspension in the melt, the carbon in
solution will be unable to precipitate. Thus, the melt will
continue to undercool until the undercooling nally
becomes sucient to provoke precipitation on some
other (less favorable) substrate. Only relatively few such
nuclei will operate, activating in those parts of the melt
that are especially cool, such as those regions close to
VOLUME 40B, DECEMBER 2009791

the mold walls. The subsequent evolution of heat will

inhibit other nuclei from becoming active. All the
coupled eutectic forms described below are therefore
not especially inuenced by the (rather rare) nucleation
events. They are mainly inuenced by the continuous
growth process.
At modest undercoolings, the coupled growth takes
the form of rosettes, which are often called cells
(Figure 8).[40,41]
Thus, it seems likely that a single initiation event on a
nucleus, which is often sited on the mold wall, expands
the coupled growth front as a hemisphere to form the
rosettes, or cells (Figure 8). The cells are beautifully
regular structures with interake distances now strictly
controlled by diusion in the boundary layer immediately ahead of the advancing front. Whether the rosette
form is a strictly coupled growth, not requiring the
presence of bilms, is not clear. For instance, it may be
some kind of aggregate of bilms that, the graphite
having nucleated, subsequently develops along radially
oriented bilms to generate the appearance of a single
growth phenomenon. Those bilms present between
akes, at less than a diusion distance from neighbors,
will lose any graphite to their neighbors by a natural
coarsening process, and so these bilms become invisible. Thus, a clearly formed rosette structure may be
capable of generating from a random morass of bilms.
A careful examination of graphite akes to determine
whether they contain bilms, and an examination of
interake regions to check for bilms, will help to settle
such questions.
At lower undercoolings, ner, more highly undercooled eutectic, which is sometimes designated Type D
or E according to ASTM specication A247, seems in
general to have been avoided for general engineering
castings. This is possibly because the interake diusion
distance is now so small that only ferrite can be formed,
limiting the strength of such irons.
During coupled growth, akes have to realign their
growth direction continually because of the intrusion of
their neighbors into their growth space. Because the

Fig. 8A scanning electronic microscope (SEM) image of a deeply

etched rosette of ake graphite, expanding to form a cell (courtesy
of Fras et al.[40,41]).
792VOLUME 40B, DECEMBER 2009

growth direction of graphite is mainly parallel to the

basal (0001) plane, this means that the crystal has to
develop faults to allow it to change direction. Probably
all coupled eutectic graphites experience this eect.
However, in particular, this explains the coral type of
graphite morphology (to be discussed later), which is
highly faulted.[42]
We would expect, therefore, that ne graphite morphologies, types D and E graphite, would be highly
faulted, containing high defect densities, whereas rosette
(or cell) graphite would represent an intermediate case
as a result of its larger spacing. Primary ake graphite,
as mentioned above, would be expected to contain the
least faults.

VI.

SPHEROIDAL GRAPHITE IRON (SGI)

(DUCTILE IRON)

When sucient magnesium is added to the melt, the

oxide bilms are completely eliminated. In the case of
silica-rich bilms, the silica will be reduced by magnesium to (1) silicon metal, which will dissipate into
solution in the matrix, and (2) solid magnesium oxide
that will precipitate probably on the pre-existing nuclei
that originally sat on the lms, augmenting these
original particles. The reaction is simply
SiO2 2Mg Si 2MgO
The total loss of bilms means that only solids remaining in suspension in the melt are the original particulate
nuclei, possibly augmented by additional MgO. If sulfur
is also present in the melt, then the MgO is likely to
contain a component of MgS. These compact nuclei are
now the only nucleation sites available for the precipitation of graphite. The precipitating graphite grows
over the compact nucleus, wrapping completely around
it so as to form a compact initiating morphology.
The disappearance of the bilms and the initiation of
spheroids are shown schematically in Figure 9. The
wrapping around process (Figure 9(d)) may consist of
renucleation of many separate microscopic grains of
graphite on favorable fragments of the oxysulde surface. The growth mode is probably some kind of addition
of carbon atoms to spiral growth steps generated by
h0001i oriented screw dislocations (Figure 10).[43] In this
way, the radial structure of graphite nodules develops
from the graphite grains growing radially out from the
compact nucleus to form the familiar approximately
spherical nodule (Figure 11).[44]
The careful study by Riposan[16,17] on ake graphite
irons shows that the particulate nuclei do not seem, in
general, to be completely wrapped around by graphite,
but graphite forms preferentially on isolated regions of
the particle. On the one hand, if such a behavior also
exists for ductile iron, as seems possible, then this
unpromising start to nodularity will emphasize the
possible importance of plastic constraint of the surrounding austenite matrix as will be discussed below. On
the other hand, the addition of Mg, in addition to
eliminating the silica-rich bilms, might also somehow
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 9(a) The melt with bilms and sundry contaminant or preconditioned nuclei; (b) the elimination of the silica-rich bilms by addition of
Mg; (c) the survival of existing nuclei and additional nuclei from inoculation; (d) the nucleation of graphite, wrapping completely around existing nuclei (particularly if they happen to pass through constitutionally supercooled regions); (e) growth of spheroids.

Fig. 10The probable structure of a graphite nodule.[43]

aect the ability of the nuclei to work more eciently, so

that a complete wrapping around eect might be
promoted. Subsequent research will clarify this point.
Later, as the graphite grows, Stefanescu[45] concludes
in his review that all the evidence points to nodules
initially growing freely in the liquid, subsequently
developing a shell of austenite, and nally contacting
and becoming incorporated into an austenite dendrite.
A minor modication of this development may be
envisaged, in which the graphite nodule does not grow a
shell of austenite until it contacts an austenite dendrite.
At that moment, a shell of austenite would be expected
to wrap itself rapidly around the nodule. Painstaking
metallography would be required to clarify this detail.
Anyway, whatever the ner details of the encapsulation
process, the shell of austenite seems a key feature
associated with the growth of spheroids.
It seems possible that the spherical morphology of the
graphite nodules may be encouraged by the mechanical
constraint provided by the nodule having to force its
growth against the resistance provided by its surrounding shell of austenite.[46] Many studies have clearly
revealed the deformation of austenite dendrites by the
growth of internal nodules (Figure 12).[47]
This lumpy morphology has been attributed to
various mechanisms, all of which are likely to contribute
to some degree, as follows:
(a) Ruxanda et al.[48] and Stefanescu[45] assume the
protrusions to be the natural growth shapes arising
from cooperative growth of austenite and graphite
by diusion from the liquid.
(b) Buhrig-Polackzed and Santos[49] indicate in a schematic illustration that the contact between nodules
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 11Graphite nodules in an austempered iron indicating nucleation on a small central inclusion.[44]

with their austenite shells and the austenite dendrites

results in their mutual assimilation, to create a
local bump on the dendrite. (Some subsequent surface smoothing driven by surface energy would be
expected to occur rapidly.)
(c) Deformation of the dendrite by plastic ow, locally
expanding the surrounding solid to accommodate
the increasing volume occupied by the graphite has
to be important. This eect seems to have been
generally overlooked, but it is important and worthy
of examination, as discussed below.
The pressure developed in a thick spherical shell
(Figure 13) expanding plastically because of internal
pressure is quantitatively expressed by[50]
P 2Y ln b=a

1

where P is the internal pressure, Y is the yield stress, and

b and a are the external and internal radii of the shell,
VOLUME 40B, DECEMBER 2009793

Fig. 12The distortion of dendrites as a result of the internal growth of nodules (after Hillert[47]).

Fig. 13A thick shell expanding plastically because of internal pressure. A perturbation radius r is not favored because a higher local
pressure is required. Thus, sphericity is encouraged.

respectively. The logic is as follows: If a perturbation to

the spherical graphite shape were to occur, having a
necessarily smaller radius r, the pressure to extend
plastically the growth at this location would (according
to Eq. [1]) be increased (Figure 12(b)). Thus, growth of
the extension of smaller radius would be discouraged
because additional pressure would be required to
stabilize the perturbation. The easier spherical growth
mode, simply expanding the uniform radius a, would
therefore be encouraged. It seems, therefore. that there
is some qualitative justication for believing that
mechanical forces stabilize the spherical growth mode
of the nodule.
However, it is useful to ascertain whether there is
quantitative justication for this mechanism. If we take
Y to be approximately 6 MPa[51] for austenite at the
melting point of iron, and a = 2 nm and b = 20 nm,
then we nd P = 30 MPa approximately. Even at
values of a = 20 lm and b = 200 lm, P is of course
unchanged, which indicates that there is a substantial
restraining pressure on the growth of the nodule during
most of its life.
With regard to the possible asymmetric eect of a
perturbation of radius r, taking r = a/2 to a/10 locally
increases P to approximately 35 to 60 MPa, respectively.
Thus, a rounding eect caused by mechanical smoothing

794VOLUME 40B, DECEMBER 2009

of the forces to expand the austenite shell seems to be

important. Although a creep model rather than the
above plastic model might give a somewhat more
accurate result, the above result can be relied on to give
us an order-of-magnitude estimate of the eect. Clearly,
more work is required to conrm this preliminary
indication.
Johnson and Smart[35] use the sophisticated and
respected perturbation analysis by Mullins and Sekerka
to suggest that interfacial energies are of importance in
spherodizing graphite nodules up to a diameter of
perhaps 50 nm, after which the spherical form can no
longer be stabilized. Thus, much speculation by earlier
authors that interfacial energies may be important in
dening the shape of spheroidal graphite seems irrelevant. This leaves mechanical stabilization as a potential
critical mechanism. This conclusion is reinforced by the
recent evidence[16,17] that the early phases of growth of
the graphite around the nucleus are anything but
regular. Clearly, a strong spherodizing eect is needed
that neither the nucleation mechanism nor surface
energy can provide.
In general agreement with this conclusion, Jiyang
et al.[52] used color etching to reveal the austenite shells
around graphite. They found that if the shell formed
quickly and completely, then the nodule developed as a
sphere, whereas slow-developing or nonenveloping
shells led to misshapen nodules.
In passing, it may be signicant that on the addition
of Mg causing dissolution of the silica-rich oxide bilms,
any residual air trapped between the lms is expected to
be released. The air trapped in a bilm will be expected
to lose its oxygen by continued oxidation of the matrix,
followed by nitrogen that would react to form nitride,[53]
leaving mainly argon. In this way, it seems possible that
clouds of ne argon bubbles will be released into the
melt. It seems likely that some Mg vapor will also diuse
into the bubbles. It is not easy to dene the sizes of such
bubbles with any accuracy. For instance, a bilm of
100 lm square and an average gas gap of 1 lm would
yield a pore of approximately 20 lm diameter. A similar
area bilm of an average 10-nm gas gap would form a
pore approximately 5 lm in diameter. A small bilm of

METALLURGICAL AND MATERIALS TRANSACTIONS B

10 lm square and 10-nm average spacing would create a

1-lm-diameter pore. Thus, it seems that a fog of bubbles
in the range of approximately 1 to 20 lm is to be
expected.
It is intriguing, but not perhaps relevant, that a theory
proposes that nodules nucleate from Mg bubbles in
suspension in the melt.[54,55] However, attractive this
hypothesis might be to explain graphite coatings inside
pores in solidied castings, as a result of the reduction in
strain energy involved, any strain energy relief in the
liquid state is zero, and the reduction of surface energy to
encourage such precipitation in the liquid state seems
negligible. Furthermore, the theory requires the incorporation of solid particulate oxide nuclei into the bubble,
but a successful penetration of a particle into the bubble
would depend critically on a reduction in interface
energies. This is unlikely for particles formed by precipitation in situ in the liquid, which will be in perfect atomic
contact with the melt (i.e., will be well wetted, which is
a necessary condition for the particle to be a nucleating
agent). Such particles will be energetically rejected by
bubbles. Thus, although a mechanism for the presence of
extremely ne bubbles may be provided by the current
analysis, it seems to be irrelevant to the formation of
graphite nodules. It does not oer support to the gas
bubble nucleation hypothesis.
Another interesting aside can be noted. The transformation of the planar cracks sandwiched inside the
bilms into clouds of ne bubbles that may oat and
escape from the alloy is the essence of the process by
which apparently brittle gray iron becomes ductile.
(Ductile iron only becomes embrittled once again, as
noted below, if oxide bilms are reintroduced by
turbulence by handling of the melt or poor lling system
design of the casting.)
Finally, curious observations, such as that reported
by Yamamoto et al.,[56] in which ake is converted into
nodular iron by simply purging the melt with ne
bubbles of nitrogen, argon or carbon dioxide become
explicable. From experience in the light metals industries, it is known that purging with gases can eliminate

bilms from melts. Thus spherodization seems to be

achievable via a purely mechanical route, replicating
the condition achieved chemically by the addition of
Mg.

VII.

COMPACTED GRAPHITE IRON (CGI)

If the addition of magnesium is more carefully

controlled to some level intermediate between spheroidal and ake iron, compacted (vermicular based on
the Italian for worm-like) graphite is the result
(Figure 14).[57]
In our bilm model, it is clear that most of the oxide
bilms will be dissolved by the addition of Mg.
However, small patches may remain if the Mg addition
is not too high; the tiny patches on which the original
nuclei sat will be resistant to dissolution because they
will be stabilized by their attachment to the nuclei.
(Naturally, it will have been energetically favorable for
the nuclei to attach to the bilm, so that the combination of nucleus and lm will enjoy a reduction in overall
energy, stabilizing the combination.) Only half of the
bilm will be retained in this way, its distant twin half
not enjoying the protective inuence of the nucleus will
dissolve and disappear. Only the small part of 1/2 of the
bilm together with its unbonded interface, the remnants of the layer of air, will remain (Figure 15(b)).
The subsequent nucleation of graphite on the nucleus
will result in rapid spreading of growth around the
nucleus. On arrival at the nonwetted interface of the
residual patch of bilm, this spreading will be arrested
(Figure 15(c)). The subsequent growth of graphite is
forced to occur not radially but in general unidirectionally away from the bilm residue (Figure 15(d)).
Clearly, the growth cannot now be a ake because no
bilm is present. Originally, it was thought that it could
not be spherical because it could not encapsulate the
complete nucleating particle, but the observations by
Riposan[16,17] and others indicates that the nucleating
particle is often not entirely surrounded in the case of

Fig. 14CGI viewed by (a) SEM deep etching and (b) optical metallography.[57]
METALLURGICAL AND MATERIALS TRANSACTIONS B

VOLUME 40B, DECEMBER 2009795

Fig. 15The formation of CGI by addition of just enough Mg to (a) melts with existing bilms with attached nuclei, to (b) eliminate most of
the silica-rich bilms, but not the remnant of lm attached to the nuclei. (c) Inoculation promotes graphite growth on the nuclei; (d) growth continues unidirectionally.

ake iron, and this may also be true of nodular iron.

Naturally, the subsequent growth form is not possible to
predict and has to depend on completely dierent
factors. With regard to the microstructure of growth,
Cole[58] had observed a ne, unidirectional spiral structure similar to the worm-like growth mode clearly
observed in Figure 14. Liu[59] nds that the growth
direction is along the C axis (0001 direction perpendicular to the basal planes) and seems to develop by a spiral
dislocation mechanism as witnessed by the coarse and
irregular spirals that they observe.
The great sensitivity of the compacted graphite
morphology to magnesium concentration is corroborated by the proposed bilm mechanism. If the Mg level
is too low, then residual bilms will encourage ake
graphite, whereas if the Mg level is too high, then the
limited stability enjoyed by the residual bilm patches
will be overcome, and the last remaining patches of
bilm will be dissolved, encouraging the growth of
totally spherical grains.
Clearly, the nal form of CGI is not strongly
inuenced by the inoculation and nucleation events. It
develops its continuous worm-like growth because of a
continuous growth process. As an important feature of
the continued growth of CGI, several workers nd that
the graphite seems to stay in contact with the liquid (for
instance, References 60 and 61), thus transferring the
expansion of the graphite to the liquid, reducing feeding
requirements,[62] in contrast to ductile iron in which the
graphite transfers its expansion to its surrounding
solidied shell, expanding the casting and increasing
feeding requirements.

VIII.

CORAL GRAPHITE

Coral graphite is, as its name suggests, a brous

morphology of graphite, formed in rather pure, noninoculated irons. Because of the purity of the alloys, and the
fact that it can be grown in alloys containing Ce, no silicarich oxide bilms can be present. The purity and absence
of inoculation also means that no oxysulde nuclei are
present. Thus, neither akes nor spheroids can form.
Thus, coral graphite occurs at high undercoolings
(clearly at least one nucleation event is required, but the
796VOLUME 40B, DECEMBER 2009

Fig. 16An SEM image of deeply etched CGI closely resembling

coupled eutectic coral structure, illustrating the overall similarity of
these structures (Courtesy of Thomas Prucha, AFS, 2009).

phenomenon is dominated by growth). After initiation

in undercooled regions, the growth of the eutectic is
likely to be so fast that it will cover large undercooled
regions at the mold wall, thus advancing subsequently
on a substantially planar growth front away from the
wall. This seems to be a coupled growth mode.
For interested readers, even though nowhere in their
report do Nakae and Shin[5] mention coral graphite,
they present micrographs that clearly illustrate coral
growth when the iron is suciently pure, or Ce is added,
and when the growth rate is suciently high. They show
the close similarity between the coral eutectic structures
of Fe-C and Al-Si alloys.
CGI and coral forms of graphite (Figure 16) are both
ne, brous lamentary morphologies. It is tempting to
consider that the resemblance reects an underlying
similarity.

IX.

MISSHAPEN SPHEROIDS

The presence of ill-formed spheroids, particularly if

present in large numbers, is widely known to be
associated with the reduction in mechanical properties

METALLURGICAL AND MATERIALS TRANSACTIONS B

of nodular irons. Hughes[44] describes how a good

ductile iron can achieve at least 90 pct nodularity but
less good irons can fall to as low as 50 pct or less and
suer reduced properties. The 50 pct or so component
of akes or other non-nodular shapes does not particularly aect properties such as proof strength but
greatly reduces those properties sensitive to failure, such
as tensile strength and ductility. Hughes,[44] in common
with widely held belief, attributes this loss of fracture
resistance to the sharp notches at the root of akes.
However, this belief presupposes that the akes act as
cracks. This would not be true if graphite had high
tensile strength perpendicular to its basal plane but is
probably only true if the akes are formed on bilms;
the bilm provides the unbonded interface, as a crack. It
is the presence of the crack provided by the bilm that
has to be viewed as the principal cause of failure.
In terms of the bilm hypothesis, graphite would be
expected to grow on oxide bilms. During the Mg
treatment, the silica-rich bilm content of the melt
would be eectively eliminated. Thus, in a liquid now
cleaned from transient silica-rich bilms, spheroids
would be created in suspension. However, many Mg
addition techniques are extremely turbulent, so that
large quantities of Mg oxide and/or Mg silicates are
expected to be created by the turbulent jumping and
splashing of the liquid surface, thereby folding in the
oxide surface of the liquid to create entrained bilms.
These new bilms will be permanent defects formed
from highly stable magnesia or magnesium silicate.
Prior to pouring, some of these will fortunately oat
out, adding to the Mg-rich slag. Thus, given a reasonable time between Mg treatment and the pouring of the
castings for separation of Mg-rich bilms (an interesting
and clearly important process variable that seems not
well researched), not all of these defects will nd their
way into the castings to impair the structure and
properties.
Unfortunately, on pouring into the mold, additional
large quantities of Mg-rich oxide bilms are likely to be
reintroduced, particularly if the mold lling system is a
rather poor design.
On contact with an oxide bilm, the subsequent
growth of the existing suspended spheroids will be
redirected along the plane of the lm. The symmetrical
spherical constraint previously provided by the surrounding austenite is also destroyed, aiding the nonspherical development. Thus, the spheroid will grow to
become signicantly misshapen.
This eect can be observed in Figure 2. In this gure,
several oxide bilms have been straightened by the
growth of dendrites so as to lie along 100 planes. These
planes, now containing a planar bilm crack, lead to
disastrous brittleness known as plate fracture (Figure 1)
described elsewhere by the author.[3] Meanwhile, the
nodules attached to the bilms are clearly poorly
shaped. Additional misshapen nodules are evident
elsewhere in the structure. These are expected to be
lying on random areas of bilm not straightened by
dendrite growth.
The appearance of poorly shaped spheroids is therefore
predicted to be associated with the growth of nodules on
METALLURGICAL AND MATERIALS TRANSACTIONS B

bilms as a result of either (1) insucient dwell time for

the damage introduced during Mg addition to oat out,
or (2) poor casting practice, in which an otherwise nicely
inoculated and spherodised melt is recontaminated with
oxides. It is interesting to predict that perhaps more time
after the spherodizing treatment to allow the melt to clear,
together with a properly designed lling system, or
counter-gravity lling system, should completely eliminate poor nodularity.
A step in the right direction is presented in the work of
Takita et al.,[63] who observe that nodules are converted
from misshapes to spherical by the use of a lter to take
out the inclusions produced by inoculation. This
positive step contrasts with that taken by Liu et al.[64]
who, after the Mg addition, added post inoculants.
These were highly successful to increase the nodule count
but led to a disastrous fall in nodularity. This was almost
certainly a result of adding the inoculants through the
melt surface, which would have also entrained the
surface oxide to create Mg-rich oxide bilms that, on
contact, would generate nonspheroids.
Furthermore, of course, the signicant reduction of
properties associate with malformed spheroids cannot
be the direct result of the shape of the spheroids, because
they occupy such a small volume fraction of the alloy.
The loss of properties is predicted to be the result of the
presence of the bilms in the melt, occupying a vastly
greater cross sectional area than the spheroids. These
extensive bilms simply act as cracks in the casting,
signicantly reducing properties.

X.

EXPLODED NODULAR GRAPHITE

Exploded spheroids (Figure 17)[65] are commonly

observed in irons subject to graphite otation and
especially if the composition of the iron is suciently
hypereutectic.[66,67]
This undesirable morphology is not easily explained
at this stage as a result of relatively little experimental
work to clarify the problem. Cole[58] suggested they had
suered remelting as a result of being carried by
convection in and out of hot zones of the liquid. This
seems most unlikely, however, because if the nodule had
grown uniformly in a compact morphology, then the
uniform graphite would be expected to have a substantially uniform rate of dissolution; solidication and
remelting would be expected to be reversible.
Because exploded nodules appear exclusively in the
otation region of hypereutectic irons two far more
likely factors are as follows:
(a) Nodules growing in a suciently hypereutectic
melt[66] will experience an enhanced driving force for
growth because of the carbon supersaturation that
develops as the melt cools. This will encourage
growth instabilities leading to dendritic rather
than planar growth, leading to exploded rather
than smooth spheroid surfaces.
(b) Austenite will be less likely to form in hypereutectic
irons, especially in conditions of carbon enhancement by segregation during cooling in the liquid
VOLUME 40B, DECEMBER 2009797

Fig. 17(a) Spheroid and (b) malformed spheroid; (c) chunky graphite (after Liu et al.[65]); (d) SEM iron image of an exploded spheroid;
(e) electron image.[58]

phase. The nodules may have nucleated early in the

liquid phase and grown without the benet of the
mechanical constraint of the austenite. When not
pressurized to remain spherical, the nodule will
be free to grow more like a dendrite, developing
instabilities that grow into projections to its growth
front, nally developing the characteristic exploded
forms. Evidence for mechanical restraint as a
powerful eect is presented in the section on nodular
graphite above.

XI.

CHUNKY GRAPHITE

Chunky graphite is often observed concentrated in the

centers of heavy sections of nodular iron castings.
Chunky is not a particularly helpful descriptive adjective for this variety of graphite. Its chunkiness is only
apparent under the microscope at high magnication;
otherwise, it simply appears to be ne, irregular,
branched, and interconnected fragments (Figures 17(c)
and 18).[68]
Once again, the properties of nodular iron are
reduced. However, it seems the loss of properties is
possibly more associated with the short diusion distances between branches of the graphite laments,
promoting the development of ferrite.[65]
Liu et al.[59,65] nd evidence that chunky graphite
grows along the C-axis direction, as does nodular
graphite. Furthermore, they report observations on
spheroids that exhibit gradual degeneration, which
slowly take on the growth forms of chunky graphite.
798VOLUME 40B, DECEMBER 2009

Fig. 18Graphite nodules and areas of ne, chunky graphite in the

thermal center of a 200-mm cube.[68]

Thus, they conclude that chunky graphite is a degenerate form of spheroidal graphite, and their work
implies that chunky graphite grows out from spheroids.
Itofugi and Uchikawa[69] conrm the identical growth
orientations of spheroidal, compacted, and chunky
graphites.
All these workers observe the characteristic form of
chunky graphite, as an apparently stop/start growth
in the C-direction consisting of nearly separate pyramidal chunks linked by a narrow neck, like beads on a
branching string. The individual chunk sections are
composed of layers parallel to the basal plane, but only
METALLURGICAL AND MATERIALS TRANSACTIONS B

nanometers thick. This characteristically lumpy growth

may be the result of a pulsating or irregular advance of
the growth front, with the austenite advancing to grow
nearly over the top of the graphite, forming the nearly
pinched-o neck of the graphite, only to be overtaken
again because the carbon in solution will now build up
in the liquid ahead of the front, accelerating the next
phase of growth of the graphite until the local carbon
concentration is depleted once again, and so on.
Observations by Kallbom et al.[68] seem consistent
with an origin associated with bilms. They observe the
chunky graphite to be concentrated in the center of
heavy sections, which is explained by the growth of the
freezing front pushing bilms ahead by their observations of stringers of graphite nodules. These features
are almost certainly sheets of oxides decorated with
graphite nodules that have been nucleated on the oxide
(analogously to those observed in Figure 2). They
conclude that a collaboration among Mg, S, and O is
important for chunky graphite formation.
Although the above authors provide evidence that
suggests the presence of bilms, it seems possible that at
the same time there is likely to be an absence of nuclei.
This is because so much time is available for particles in
suspension to oat out from the centers of heavy
sections where chunky graphite is commonly found. In
the absence of nuclei, spheroids cannot form. Thus, if a
graphite nodule can be initiated somewhere in or near
this region, perhaps happening to oat into this region,
it will continue to grow. However, it will not enjoy the
benet of the presence of an austenite shell in a region of
higher temperature and enhanced segregation, so that its
growth mechanism seems likely to be asymmetrical.
Because the growth will constitute an extension of the
spheroid, the spheroidal mechanism of growth along the
C-axis is likely to be continued.[59] In the absence of
signicant numbers of nuclei, the whole region will ll
with a variety of continuous, branching growth, extending along the C-axis direction. The extended size of
chunky graphite regions, which are much larger than
cells of other types of graphite,[69] corroborate the
absence of nuclei in these regions.
If the above mechanism is correct, then exploded
spheroids can be viewed to be a similar growth mode to
chunky graphite, both originating from spheroids.
However, why continued growth should not occur in
all directions as in the exploded variety, but only in a
few select directions (possibly one direction) in chunky
graphite, is not clear at this time.
It is hoped that in the near future, the correct
explanation for the origin of chunky graphite might be
elucidated by subsequent careful experiments. The key
word here is careful. For instance, the experiment by
Asenjo et al.[70] that involves the placement of inoculants in dierent branches of a runner system to
dierent sized cavities in a mold to compare the eects
of mold inoculation in dierent heavy castings was a
clever concept but regrettably awed in execution. This
was because, in common with most iron casting, the
runners were not designed to be pressurized and ll on
a single pass. Thus, a reverse ow is likely to have
contaminated the mold cavities, and all the cast
METALLURGICAL AND MATERIALS TRANSACTIONS B

material would have suered from turbulence and air

entrainment, therefore containing unknown quantities
of oxide bilms. Clearly, in the future, much greater
sophistication of melting and casting will be required
for experiments designed to clarify the solidication
mechanisms for cast irons.

XII.

IRON CARBIDE (CEMENTITE)

Work by Rashid and Campbell[71] has demonstrated

the nucleation and growth of carbides on oxide bilms
in vacuum-cast Ni-base super-alloys. It would be
expected, therefore, that an analogous reaction would
occur in Fe-C alloys, because the austenite forming
during solidication also possesses a closely similar facecentered-cubic structure, and other conditions, such as
the temperature and solidication rates, are all similar.
Carbides in irons seem to form preferentially at grain
boundaries and often seem to be associated both with
residual graphite (sometimes as nodules, malformed
nodules, or akes aligned with the boundary) and pores
all forming on the same boundaries. This is a clue to
their bilm associations.
Faubert et al.[72] have studied carbides in heavysection austenitic ductile iron (ADI). Toward the top of
their castings, they nd degradation of properties more
serious than they would have expected from the carbides
themselves. They suspected that the real impairment was
caused by the presence of lms that had oated into this
region. Almost certainly, the lms would have been
bilms (it seems impossible to devise a mechanism by
which a single thickness of lm can be introduced into a
matrix). Bilms would segregate to grain boundaries
and possibly actually constitute the boundary. The
presence of the bilm is not only inferred from (1) the
cracked carbides but also (2) from the linear rows of
nodules viewed in micrographs from this work, (3) from
the pores as the residues of air bubbles trapped between
the lms, and (4) from the graphite akes sitting in the
boundary (called by the authors, unatteringly, degenerate graphite). Both graphite and carbides are
expected to form on the wetted, outer surfaces of the
bilms. The presence of the central unbonded region
(including the pores) between the lms, constituting the
crack through the interiors of the carbides, explains the
apparent brittleness of the carbides. These intermetallic
compounds would otherwise be expected to be strong
and resistant to failure by cracking at the modest
stresses that can be induced by solidication and
cooling.
Stefanescu[43] quotes the work of Hillert and
Steinhauser,[73] in which the growth of iron carbide
eutectic (ledeburite) occurs by the spreading of carbide
(cementite) across a plane, followed by the development
of a rod type of eutectic at right angles. It is tempting to
consider that the original planar expansion would have
been facilitated by growth across the surface of a bilm.
The bilm would originally have been randomly crumpled but would have been straightened by the progress
of the carbide across its face, thus creating an essentially
planar crack that would constitute a serious defect in the
VOLUME 40B, DECEMBER 2009799

carbide. Associated branching cracks would have arisen

from irregular folds in the bilm.

XIII.

GENERAL

Overall, both nucleation and growth mechanisms

inuence graphite morphology, although these mechanisms dominate to dierent extents in dierent circumstances. For instance, nucleation dominates the
formation of spheroids and deformed spheroids, whereas
for ake graphite, both nucleation and growth are
inuential. For compacted, undercooled coral and
chunky graphites, nucleation occurs once to initiate each
cell, after which continuous growth leads to developing
continuous branching morphologies. Indeed, the ner,
fairly continuous forms of coral, chunky, and compacted
graphites are so similar that they often seem to be
confused in the casting literature. They do seem similar in
the sense that they all appear to be more-or-less coupled
growth forms, advancing together with the austenite.
If, as proposed here, the various forms of graphite are
signicantly inuenced by the presence or absence of
bilms, then it would explain the historical resistance of
the phenomenon to explanation so far. This seems
typical of bilm phenomena.
Furthermore, it seems likely that the principle cause
of reduced mechanical properties in all cases of nonspheroidal forms of cast irons is the presence of various
kinds of oxide bilms that act as cracks. Ductile iron is
ductile because of the absence of oxide bilms, not
because of its spherical graphite morphology; but when
oxide bilms (mainly magnesia-rich) are entrained by
poor casting technology, ductile iron can be seriously
reduced in ductility, with castings at times even failing
disastrously by the brittle plate fracture mechanism.[3]
Naturally, this short account presents only an outline
of a new approach to the structures of cast irons. Much
more research is needed to prove, enhance, or disprove
these proposals. It is hoped that improved control and
improved castings will result from these eorts.

XIV.

CONCLUSIONS

6.

7.

8.

9.
10.

growth morphology may be natural but is additionally encouraged by the mechanical constraint of
the austenite matrix; the absence of bilms explains
the high mechanical properties.
Coral morphology nucleates on unknown nuclei at
low temperatures, expanding to form cells of coupled growth with austenite, consisting of highly
faulted continuous branching laments of graphite
in the austenite matrix; bilms play no part in this
growth mode.
Misshaped spheroids seem to be spheroids that have
encountered a Mg-rich bilm, subsequently growing along the bilm and losing sphericity (Figure 2).
In addition, the presence of the bilm destroys the
symmetrical mechanical constraint of the austenite
that favors sphericity.
Chunky graphite occurs in heavy-section ductile
iron regions. The formation mechanism is not
clear at this time. The central regions comprise
either (1) regions containing Mg-rich bilms as a
result of poor casting techniques or (2) regions from
which nuclei have oated out, leaving regions nearly
devoid of nuclei and creating graphite akin to coral
morphology. As such, it may be a coupled eutectic
form, and its beads on a branching string morphology may result from an unstably advancing
growth front.
Exploded spheroids may be the result of growth in
the liquid, without the benet of the mechanical
constraint of an austenite shell.
Carbides form at low temperatures on oxide bilms.
The presence of bilms in the carbides explains the
brittle behavior of these strong intermetallics and
their common association with both pores and
residual graphite fragments.

ACKNOWLEDGMENTS
The author is grateful to those who have assisted
with the micrographs; to Carl Loper and Riposan and
colleagues for inspiring research; and, last but not
least, to the painstaking, assiduous, and doubtful
reviewer of this article from whom I learned much.

A hypothesis is proposed as follows:

1. Cast iron melts normally contain double lms
(bilms) in suspension.
2. Inoculation produces oxysulde particles that
nucleate on silica-rich oxide bilms.
3. Graphite nucleates on the oxysulde particles and
grows, spreading over the bilms, straightening the
bilms, and forming akes of crystallographically
near-perfect graphite. The presence of the bilms,
as cracks, trapped inside or alongside graphite
akes accounts for the poor tensile properties of
ake irons.
4. Compacted graphite forms on oxysulde nuclei that
occupy bilm residues.
5. Spheroids form in the absence of silica-rich bilms,
nucleating on oxysulde particles. The spherical
800VOLUME 40B, DECEMBER 2009

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