Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

A New Approach to Graphite Nucleation Mechanism in Gray Irons

Iulian Riposan, Mihai Chisamera, Stelian Stan, Torbojorn Skaland
Politehnica University of Bucharest, Romania, Elkem, Norway

Copyright © 2005 American Foundry Society

ABSTRACT

A complex research program involving the Scanning Electron Microscopy (SEM) has been undertaken in order to achieve a
more detailed understanding of graphite nucleation in un-inoculated and High Purity (HP)-FeSi, Ca-FeSi and Sr-FeSi treated
irons at different residual aluminum(Al) levels (0.001…0.05% ) in iron melt. (Mn,X)S compounds, usually less than 5.0 µm
in size, with an average 0.4-2.0 µm well-defined core (nucleus), were found to be important sites for graphite nucleation in
gray irons. Al contributes to the formation of Al2O3-based sites which act as nucleation sites for (Mn,X)S compounds, even
at a very low Al level (<0.003%) in iron melt. Increasing the residual Al content in iron melt helps the initiation of graphite
nucleation at a lower undercooling degree. A 0.005-0.01% Al content in melt appears to be beneficial, without the
detrimental effect on pinhole occurrence in gray irons. Calcium (Ca) is present in most (Mn,X)S compounds and at similar
levels in the core and shell (higher level in Ca-FeSi treated irons), while strontium (Sr) was found mainly in the core and only
in Sr-FeSi treated irons. A three-stage model for the nucleation of graphite is proposed: 1) small Al2O3-based sites are
initially formed in the melt; 2) complex (Mn,X)S compounds nucleate on these microinclusions and 3) graphite nucleates on
the sides of the (Mn,X)S particles which have a lower crystallographic misfit with the graphite. In inoculated irons, the
(Mn,X)S compound is more complex, at a lower Mn/S ratio and a higher compatibility to graphite nucleation, especially as
inoculating elements (Ca, Sr, etc.) contribute.

Keywords: gray irons, (Mn,X)S, graphite nucleant, Al-key role, optimum Al-range, Ca/Sr distribution.

INTRODUCTION

The initiation of graphite nucleation during the solidification of all commercial cast irons generally requires a nucleation site
with specific peculiarities in each case. Residual graphite should be an ideal nucleant for the formation of graphite during
solidification, but sulphide and oxide/silicate microinclusions, formed in the molten iron (Fig. 1), are also possible sites for
the heterogeneous nucleation of graphite.

Due to their hexagonal crystallographic symmetry, their favorable wetting properties, a sufficient lattice disregistry
acceptance and their high thermal and chemical stability, silicate particles are apparently the favored nucleation sites. The
ability of sulphides to nucleate graphite is hindered because these substrates belong mainly to the cubic system. However,
the nucleation potency of sulphides can be enhanced by inoculating elements (such as calcium (Ca), strontium (Sr), rare earth
(RE), barium (Ba) etc.) which can transform MnS into complex sulphides (Mn,X)S. These might have a better lattice
matching to graphite, a low coagulation capacity, good stability and adequate interfacial energy (Loper, 1998; Skaland, 1993;
Stefanescu, 1998; Chisamera, 1998 and 2000).

EXPERIMENTAL PROCEDURE

Iron melts, obtained in an acid lined induction furnace, were designed having different contents of carbon (C), silicon (Si),
manganese (Mn), sulphur (S), oxygen (O) and aluminum (Al) at different specific ratios, covering the most representative
foundry situations (Table 1). A very low level of other elements was ensured for all irons.

Experimental gray irons with typical Si concentration (1.2%) were conventionally or excessively inoculated (0.2% and 1.0%
inoculant, respectively). In addition, other irons with low Si level (0.4–0.5%) were over-inoculated by the addition of
2.0%wt inoculant in order to facilitate the detection of the inoculating elements (Ca, Sr) in the possible graphite nucleants.
High Purity (HP)-FeSi and Sr-FeSi or Ca-FeSi were used for ladle inoculation. The last two materials contain lower (0.01%),
normal (0.5-1.0%) and intentionally higher (2% ) Al content, at representative inoculating element levels (0.7-1.0% Ca or
Sr). Up to 40 ppm Ca or 30 ppm Sr were ensured in the inoculated irons.

Major experiments were the analysis of cooling curves, chill tendency, graphite size and morphology; carbides occurrence;
pearlite/ferrite ratio; eutectic cell count and size and the characterization of microinclusions as possible graphite nucleation
sites (Chisamera 2000, 2001 and 2004; Riposan 2001, 2003 and 2004).

31
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

CaO
Ce2O3 O
SrO
ZrO2 X
BaO
MgO I
Al2O3
TiO2 D
SiO2 E
MnO
S
CeS
CaS
SrS
LaS
Compound Type

BaS
MgS SULPHIDES
ZrS2
TiS
MnS
Zr N
TiN
LaN
CeN
AlN NITRIDES
Si3N4
Ca3N2
Sr3N2
Mg3N2
Ba3N2
ZrC
TiC
SiC
CeC2
LaC2
Mn7C3 CARBIDES
CaC2
BaC2
Al4C3
.

-1000 -900 -800 -700 -600 -500 -400 -300 -200 -100 0 100
Standard Free Energy,∆G0,KJ/mole(O,S,N,C)

Fig.1. This chart illustrates the standard free energy (∆Go) of the reactions for the formation of the compounds
(T=1723K).

The main objective of the present paper is the detailed characterization of the graphite nucleants (microinclusions) and a
proposition for a new view on the graphite nucleation mechanism in gray irons.

RESULTS

PHYSICAL CHARACTERISTICS OF MICROINCLUSIONS (GRAPHITE NUCLEANTS)

Depending on the degree of contact between the inclusions and the graphite, several situations were observed: a) no visible
contact with graphite (particle embedded in matrix); b) superficial contact between inclusion and graphite; c) partially
encapsulated by graphite and d) totally encapsulated by graphite. Figure 2 presents SEM micrographs illustrating these
cases.

The majority of the microinclusions, assumed to play a role in the nucleation of graphite, range in size between 1 and 8 µm,
but is usually less than 5.0 µm in diameter. The size of the microinclusions depends mainly on the cooling rate (lower size at
higher cooling rate), while inoculant type exerts a complex influence, according to other possible influence factors. In
addition, it was found that the choice of inoculant also exerts an influence on the morphology of these compounds.

Thus, the microinclusions have mainly an oval shape in the Ca-FeSi treated iron, a regular polygonal shape in Sr-FeSi treated
iron and mostly an irregular polygonal shape in the HP-FeSi treated iron (Fig.3). It can be easily observed that most of these
microinclusions possess a well-defined core (nucleus), measuring 0.1-2.7 µm in diameter but most often 0.4-2.0 µm
(Riposan, 2003). The type of inoculant affects the size of the cores of the graphite nucleants. Thus, there is a continuous
decrease in core size from un-inoculated (2.0 µm) to HP-FeSi and Sr-FeSi treated irons and to Ca-FeSi treated irons, the last
having the lowest core size (<0.5 µm). The difference (ratio) between the size of microinclusions (graphite nucleants, Dmax)
and their corresponding nuclei (dmax) is higher for irons treated with FeSi-base alloys than for un-inoculated irons. Moreover,
the Dmax/dmax ratio tends to be higher for irons inoculated with HP-FeSi than for those inoculated with Sr and Ca-FeSi.
Several typical nuclei morphologies were identified, such as regular and irregular plates; ovoid or rounded, triangular,
irregular star and square features. However, a visible dependence of the nucleus shape on the inoculant type was not
observed.

32
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

Table 1. Experimental General Procedure Parameters

VARIABLE PARAMETERS Parameters Level
1. CAST IRON CHEMISTRY
• Equivalent Carbon 3.5…4.4%
• Carbon 3.0…3.7%
• Silicon 1.0…2.2%
• Manganese 0.20…0.70%
• Sulphur 0.005…0.12%
• Mn/S Ratio 2.5…80
• Aluminum 0.001…0.05%
• Oxygen 25…100 ppm
• Nitrogen 30…50 ppm
• Calcium 1.0…40 ppm
• Strontium 0.1…30 ppm
2. INOCULATION
*Inoculant Chemistry Si,% Al,% Ca,% Sr,%
• High Purity (HP)-FeSi 73…80 <0.06 <0.05 <0.02
• Ca bearing-FeSi 73…80 0.01..2.0 0.75..0.9 0.02..0.09
• Sr bearing-FeSi 73…80 0.01..2.0 0.03..0.1 0.7..1.0
*Inoculant Addition (wt.%) 0.2…2.0
3. TESTS
*Iron Chemistry
• Base and Minor Elements POLYVAC-spectral analysis
• O,S,N LECO-analysis
• Ca, Sr Plasma Emission-analysis
*Inclusions/Graphite Nucleation Sites SEM/TEM/EPMA Techniques
-Specific Analyses Size and Morphological Features, Chemistry and Distribution
Pattern of Elements
*Cooling Curves Features NI-DAQ / NI 4350 Instrument
*Chill Tests Wedge Samples and Chill Test Samples
*Optical Metallography Graphite size and Morphology
Carbides occurrence
Pearlite/Ferrite Ratio
Eutectic Cell Count and Size

G a) b
G

G
G

c
Fig.2. Micrographs represent typical
examples of inclusions/graphite
particles distribution in gray irons
(X-ray) (G–Graphite):
a) Compo image,
b) MnKα and
c) SKα

33
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

Fig.3. These are typical morphologies of nucleants: G–Graphite; N–Nucleant

CHEMISTRY OF GRAPHITE NUCLEANTS (MICROINCLUSIONS)

Microinclusions found in superficial contact with the graphite flakes, as well as microinclusions, partially or entirely
encapsulated into the graphite flakes, were analyzed by SEM. The chemical composition distribution in different regions of
their section surface, such as the nucleus (core), compound body (shell), compound/graphite interface and compound/matrix
interface, was also measured by EDXA (Energy Dispersive X-ray Analysis).

Manganese and Sulphur

Complex (Mn,X)S compounds (Fig.2) were identified as major nucleation sites for graphite in all tested gray irons,
independent of iron melt chemistry and inoculant type and/or addition rate. Mn and S were found as the basic components of
all identified microinclusions, with a Mn/S ratio varying in the 1.3-1.7 range. These compounds are referred to as (Mn,X)S,
where X = iron (Fe), Al, Ca, Sr, Si, zirconium (Zr), titanium (Ti), phosphorus (P), etc

Figure 4 illustrates the variation in chemical composition along a line through the core of sectioned (Mn,X)S particles in
eutectic field gray irons (carbon equivalent [CE] = 4.10…4.40%). The data covers a composition range of 0.50…0.55% Mn
and 0.08…0.11%S (Mn/S = 4.5…6.8), for lower (0.001-0.002%) and higher (0.035…0.045%) residual Al content. Un-
inoculated and HP-FeSi, Sr-FeSi and Ca-FeSi treated irons (1.0wt% addition) are analyzed for both ranges of residual Al.
The compositions of the core (nucleus) and the shell (body) of complex (Mn,X)S compounds are visibly different—the core
has high levels of Al and O, while the inclusion body has high levels of Mn and S. Other elements, such as Ca, Sr and Si
present peculiar distribution.

Aluminum, Silicon and Oxygen

Strong deoxidizers, such as Al and Si, were found to be important parts of the first formed, very small, microinclusions in the
iron melt, which was believed to be nucleation sites for precipitation of (Mn,X)S particles.

As shown in Fig. 5, a visible Si-Al relationship was identified in these early formed microinclusions. At very low levels
(<0.002 wt% Al) in the iron melt the Al and Si contents are similar (up to 2.0wt%). In contrast, at more than 0.005wt%
residual Al in the iron, the Al content in the cores of (Mn,X)S compounds is more than ten times higher than that of Si
(Fig.5a). On the other hand, for more Al or Si levels, more O content in this area of graphite nucleants was found. The
highest O (>14wt%) content is typically for lower Al and higher Si (Fig.5b and 5c).

34
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

0.001 … 0.002 wt.% Al 0.035 … 0.045 wt.% Al

O Al Si S Mn Fe O Al Si S Mn Fe
100 15 100 15
core
90 90
shell core shell shell O shell

Fe, Mn, S, wt.%

80 12 80

O, Al, Si; wt.%

Fe O Fe

O, Al, Si; wt.%

70 70
Fe, Mn, S, wt.%

graphite
10
U.I 60
matrix
Fe O
matrix
9 60

graphite
matrix
Mn Al

matrix
50 50
40
Sr 6 40
Mn S Al 5
30 30
Mn
20 3 20
Si Si
10 Si S S 10 S
0 0 0 0
0 1 2 3 4 5 6 7 8 0 1 2 3 4
Distance, µm
Distance, µm

O Al Si S Mn Fe O Al Si S Ca Mn Fe
100 25 100 20

O 90

core
90 O
Fe shell core shell shell
Fe, Mn, S, wt.%

O, Al, Si, Ca; wt.%

80
O, Al, Si; wt.%
80 20
shell shell 15
70
HP - 70

Fe, Mn, S, wt.%

O matrix
graphite

Fe Mn matrix

graphite
60 15 Fe O
core

60
matrix

FeSI Mn
Fe matrix

matrix
50 50 10
40
S 10 Sr
40
30 Mn Al Mn Al
30
20 Al 5 5
20
Si
Si Si Si
10
10 Si
S S
0 0
Ca
0 0
0 2 4 6 8 10 12
0 1 2 3 4 5 6 7 8
Distance, µm
Distance, µm

O Al Si S Mn Fe Sr
O Al Si S Ca Mn Fe Sr
100 25 100 15
core
90 90

graphite

O, Al, Si, Sr; wt.%

80 20 shell
Fe, Mn, S, wt.%

shell shell 80 shell

Sr –
core
O, Al, Si, Ca, Sr; wt.%

70 O Fe O
Fe, Mn, S, wt.%

70
10
FeSi 60 matrix Fe 15 60
graphite

50 matrix Mn matrix
matrix

50
40
Sr 10 40
30 Mn 30 S 5

20 5 20
10 Si S 10
Sr Al Si
Al
0 0 0 0
0 1 2 3 4 5 6 7 8 0 1 2 3 4 5
Distance, µm Distance, µm

O Al Si S Ca Mn Fe O Al Si S Ca Mn Fe
100 15 100
24
90 90
Fe shell O shell 21
O, Al, Si, Ca; wt.%
O, Al, Si, Ca; wt.%
Fe, Mn, S, wt.%

80 80
Fe, Mn, S, wt.%

Ca - 70 70
Fe shell core shell
18
10 matrix
FeSi Fe O matrix
Fe Al O
core

60 60 15
Mn
graphite

matrix graphite
O
matrix

matrix

50 50 Mn 12
40
Sr Sr
40
Mn S 5 9
30 30 Mn S
20
Si 6
20
Ca
Si Si
10 S 10 Si Ca S 3
Al
0 0 0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 0 1 2 3 4 5 6 7 8 9 10
Distance, µm Distance, µm

Fig.4. Change of chemical composition of sectioned (Mn,X)S particles (wt%) are graphed.

35
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

Fig.5. Aluminium, silicon and oxygen relationships

in the core of (Mn,X)S compounds are shown.

Key: Figs. 5 and 6

Fig.6. Al(shell)–Al(core) relationships in (Mn,X)S compounds are shown.

36
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

It can be concluded that Si-Al-O and Al-O containing compounds are at the bases of the cores (nuclei) of (Mn,X)S
compounds for the very low (0.001-0.002wt%) and the higher (0.009-0.045wt%) residual Al content in the iron melt,
respectively.

Important Al contents were detected in all microinclusions found to have a role in the nucleation of graphite. The Al is
concentrated mainly in the core (nucleus) of these nucleants (ten times higher than in the shell), even at very low levels of Al
(0.001…0.002%) in the iron melt. The Al(shell)/Al(core) ratio exceeds 0.2 (and can reach up to 0.8) only at very low residual Al
in the iron melt, when important Si quantities were identified in the cores of (Mn,X)S compounds. In this case, the typical
levels of Al are less than 2.0wt% in the core and 0.4wt% in the shell. Increased Al content in the molten iron leads to
increased Al content in microinclusions, in both the core and shell sections—up to 23 wt% Al in the core and 1.0wt% in the
shell, for an Al(shell)/Al(core) ratio less than 0.2. Generally, lower levels of Al were found in Sr-FeSi inoculated irons than in
Ca-FeSi treated irons (Fig.6).

Calcium and Strontium

As inoculating elements, Ca and/or Sr were detected with peculiar distribution pattern in different sections of (Mn,X)S
compounds (Fig. 7 and 8). Ca is present in most (Mn,X)S compounds, including Sr-FeSi and HP-FeSi treated irons, while Sr
has a detectable presence only in the Sr-FeSi inoculated irons.

It was found previously that Ca had a quasi-homogeneous distribution over the whole particle cross-section, apparently at a
higher level in the shell than in the core. In contrast, Sr was present mainly in the core and possibly in small amounts as solid
solution in the (Mn,X)S compound body (Riposan, 2001). A more thorough analysis, using Environmental Scanning
Electron Microscope-Energy Dispersive Spectrometry (ESEM-EDS), revealed a clearer difference between the shell and core
concentrations and the shell/core distribution ratios for Ca as compared to Sr (Fig.7). Thus, Ca appears to be similarly
distributed in the shell and core, with a Ca(shell)/Ca(core) ratio of 0.5-1.0. In contrast, the Sr distribution pattern presents two
specific fields. Approximately 75% of the compounds analyzed had less than 2.0wt% Sr in the core and up to 1.5wt% Sr in
the shell, while others had up to 20wt% Sr in the core and less than 1.5wt% Sr in the shell.

It was found that the Al concentration in the core is an important influencing factor on the Sr and Ca levels in different
sections of the (Mn,X)S compounds (Fig.8). Higher Al content in the cores led to a decreased Sr concentration in the same
region, resulting typically in less than 2.0wt% Sr. In contrast, more Sr is usually present at very low Al concentrations in the
iron melt and the first formed microinclusion as well. At the same time, a higher Al content in the core is accompanied by a
higher concentration of Sr in the shell (body) of (Mn,X)S compounds.

In Ca-FeSi inoculated irons, the Ca concentration in both the core and the shell regions is favored by higher Al levels in the
iron melt and in the core of (Mn,X)S compounds. Increasing the residual Al level in the iron melt appears to favor higher
concentrations of Sr or Ca in the (Mn,X)S compounds.

GRAPHITE NUCLEATION
Based on the analysis of a large number of inclusions, the following three-stage model for graphite nucleation is proposed,
for both un-inoculated and inoculated gray irons.
Stage 1: Microinclusions containing strong deoxidizing elements, such as Al, Si, Mn, Ti, Zr etc, are formed in the melt.
Stage 2: (Mn,X)S compounds nucleate at these oxide-type microinclusions. In un-inoculated irons, X is mainly Fe and to a
lesser extent X = Ca, Al, Ti, etc., while in inoculated irons X = Ca, Sr, Al, RE, etc. A thin layer of silicate may form
at the surface of the (Mn,X)S compound in the inoculated irons.
Stage 3: Graphite nucleates at one or more (Mn,X)S compound sides. In un-inoculated iron, the (Mn,X)S compounds are
simple and the crystallographic misfit between the graphite and the compound is relatively large. In inoculated iron
(Mn,X)S compounds are more complex and the crystallographic misfit between the graphite and the compound is
lower; thus, these compounds are better suited to graphite nucleation.

Figures 2 and 3 show representative nucleation sites for flake graphite. Typical model for graphite nucleation in gray irons is
illustrated in Fig.9. A peculiar behavior is shown in Fig.3d for Ca-FeSi inoculated iron—graphite grew on the right side of
an ovoid (Mn,X)S compound, while on the left side this process was only at an incipient stage in a porous area.

37
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

Fig.7. Distribution pattern of (a, b) Ca and (c,d) Sr in (Mn,X)S compounds are shown.

Key: Figs. 7 and 8

Fig.8. Influence of Al on Sr (a,b) and Ca (c,d) distribution in (Mn,X)S compounds is shown.

38
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

1
3
2

Fig.9. This is a typical model for graphite nucleation in gray irons: (1) Al2O3 nucleus core; (2) (Mn,X)S shell
compound and (3) graphite flakes.
SURFACE TENSION, σ, [Dynes/cm]

Optimum Level
OPTIMUM LEVEL

HYDROGEN PICKUP, H, [ppm]

1000 0.005-0.010%Al 2
0.008 -0.010% Al H [Dawson, Smith]
900 1.8
800 1.6
700
H 1.4
600 1.2
PINHOLES
500 1
(σ<600)
400
300
σ 0.8
0.6
200
σ [Hernandez, Wallace]0.4
100 0.2
0 0
0.001 0.01 0.1 1

Aluminium in iron melt, %

Fig.10. Optimum Al level (0.005…0.010wt.%) according to surface tension (σ) of gray irons (normalized to 1400oC)
(Hernandez 1979) and hydrogen (H) pick-up in green sand mold (Dawson 1956, Wallace 1989) is illustrated.

AL—KEY ROLE IN GRAPHITE NUCLEATION IN GRAY IRON

As a residual element in molten iron, Al (0.001…0.5%), could have two effects in gray irons—a) traces of Al can produce
pinhole gas defects in iron castings (critical range 0.02-0.2% Al) and b) the presence of Al should influence the graphite
nucleating capacity.

It is generally considered that Al has virtually no inoculating effects as such and it is not included in the inoculating elements
group. However, this research pointed out a key role that Al plays in the graphite nucleation process. It forms Al2O3-based
sites, which act as nucleants for (Mn,X)S compounds. The later, in turn, are the major nucleation sites for the growth of
graphite flakes. In addition, Al appears to favor the presence of Sr or Ca in the shell of the (Mn,X)S compounds (Fig.8).
This also lowers the crystallographic misfit between the compound and the graphite. Under specific conditions, residual Al
also causes the decreasing of the undercooling degree and the increasing of the eutectic cell count, and favors the formation
of A-type graphite (Chisamera, 2004: Riposan, 2004).

39
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

In order to minimize the pinholing in green sand molds and to obtain an efficient graphitization process, an Al content of
0.005-0.010% is recommended (Fig.10). At this level, the surface tension of molten iron is high enough (Hernandez 1979).
The hydrogen (H) pick-up from green sand mold is limited (Dawson,1956; Wallace, 1989). This optimum level of residual
Al can be reached through all of the tested procedures—as charge materials, Al-addition as a preconditioning agent or
through FeSi-based inoculants.

Raising the Al content in an iron is useful for un-inoculated gray irons or for inoculated gray irons when the inoculation
response is inadequate (other process parameters at normal levels). If the inoculant performance is satisfactory and consistent
at lower Al levels in the iron, an adjustment of the Al content could be considered to further improve iron quality or cost
effectiveness.

CONCLUSIONS

Based on the SEM analysis of a large number of microinclusions, which are possible graphite nucleation sites, the following
main conclusions can be drawn.

(Mn,X)S compounds (where X = Fe, Al, O, Si, Ca, Sr, Ti etc) with different morphologies (regular or irregular polygonal
shape or ovoid shape) are major sites for graphite nucleation in gray irons. These compounds are 1-8 µm in size (usually
<5.0 µm) and have a well-defined core (nucleus), measuring 0.1…2.7 µm (usually 0.4…2.0 µm).

It was found that Al has the ability to contribute to the formation of Al2O3-based sites suitable for the nucleation of (Mn,X)S
compounds. This was observed even at very low Al (<0.003wt%), contents in the iron and especially in un-inoculated irons
or under less efficient inoculation conditions.

Higher Al levels in the iron result in higher concentrations of Al in the nuclei of these compounds and at a lesser extent also
in their shells (bodies). Increasing the residual Al level in iron melt is useful to initiate the graphite nucleation process. A
0.005…0.01wt% Al range appears to be beneficial for graphite formation in gray irons (type A-graphite formation, no
carbides, higher eutectic cell count, etc.) without the detrimental effect on pinhole occurrence. Under specific conditions
(higher cooling rate, very low graphitizing potential of iron melt, etc.), Al between 0.01wt% and 0.015-0.016wt% appears to
be necessary.

Ca is present in most (Mn,X)S compounds, at similar levels in the core and shell. The Ca content is promoted by the
presence of Al, especially for Ca-FeSi inoculated irons.

Sr is present mainly in the core of (Mn,X)S compounds (more Sr in the core, lower Sr(shell)/Sr(core) ratio) only in Sr-FeSi
inoculated irons. At higher Al content, the Sr concentration is lower in the core but higher in the shell.

A three-stage model for the nucleation of graphite in both un-inoculated and inoculated gray irons is proposed: 1) small
Al2O3-based sites are formed in the melt; 2) complex (Mn,X)S compounds nucleate at these microinclusions; 3) graphite
nucleates on the sides of the (Mn,X)S compounds with lower crystallographic misfit with graphite. In inoculated irons,
(Mn,X)S compound is more complex, at lower Mn/S ratio and at higher compatibility to graphite nucleation, especially as
inoculating elements (Ca, Sr, etc.) contribute.

REFERENCES

1. Chisamera, M., Riposan, I. and Barstow, M., “The Importance of Sulphur to Control Graphite Nucleation in Cast Iron,”
AFS International Inoculation Conference, paper no. 3, Chicago (1998).
2. Chisamera, M., Riposan, I., Stan, S. and Skaland, T., “Undercooling—Chill Size-Structure Relationship in the Ca/Sr
Inoculated Gray Irons under Sulphur/Oxygen Influence,” 64th World Foundry Congress, paper RO 62, Paris (2000).
3. Chisamera, M., Riposan, I., Stan, S. and Skaland, T., “Cooling Curve Analysis of the Ca/Sr Over-Inoculated Gray Iron,
at Lower Initial Silicon Content,” International Conference on the Science of Casting and Solidification, pp 330–
335, Brasov (2001).
4. Chisamera, M., Riposan, I.,Stan, S. and Skaland, T., “Effects of Residual Aluminium on Solidification Characteristics of
Un-Inoculated and Ca/Sr Inoculated Gray Irons,” AFS Transactions, vol 112, pp 867–877 (2004).
5. Dawson, J.W. and Smith, L.W.L, “Pinholing in Cast Iron and its Relationship to the Hydrogen Pickup from Sand Mold,”
BCIRA, J.Res. and Dev. 6, p 226 (1956).
6. Hernandez, B. and Wallace, J.F., “Mechanisms of Pinhole Formation in Gray Irons,” AFS Transactions, vol. 87, pp 335–
348 (1979).

40
 Proceedings of the AFS Cast Iron Inoculation Conference, September 29-30, 2005, Schaumburg, Illinois

7. Loper, C.R and Gundlach, R.B., “Inoculation What Is It and How Does Inoculation Work? AFS International.
Inoculation Conference, paper no. 1 Chicago (1998).
8. Riposan, I., Chisamera, M., Stan, S., Skaland, T., and Onsoien, M.I.,”Analyses of Possible Nucleation Sites in Ca/Sr
Over-Inoculated Gray Irons,” AFS Transactions, vol 109, pp 1151–1162 (2001).
9. Riposan, I., Chisamera, M., Stan, S. and Skaland, T., “Graphite Nucleant (Microinclusion) Characterization in Ca/Sr
Inoculated Irons,” International Journal of Cast Metals Research, vol 16, no.1–3, pp 105–111 (2003).
10. Riposan, I., Chisamera, M., Stan, S., Gadarautanu, C. and Skaland, T., “The Key Role of Residual Aluminum in Chill
Tendency and Structure Characteristics of Un-Inoculated and Ca/Sr Inoculated Gray Irons,” 66th World Foundry
Congress, pp 775–789, Istanbul (2004).
11. Skaland,T., Grong,O and Grong, T., “A Model for the Graphite Formation in Ductile Cast Irons,” Metallurgical
Transactions, 24A, 2321 (1993).
12. Stefanescu, D.M., “Inoculation of Thin-Wall Castings,” AFS International Inoculation Conference, paper no. 16,
Chicago, (1998).
13. Wallace, J.F. and Wieser, P.F., “Pinholes in Gray Iron, Elemental Effects on Gray Irons,” AFS Conference, paper II A1-
A14 Chicago (Sept 19-20, 1989).

41
42