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Formation of Complex Nuclei in Graphite Nodules of Cast Iron

Article  in  Carbon · August 2020

DOI: 10.1016/j.carbon.2020.08.022

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 Formation of Complex Nuclei in Graphite Nodules of Cast Iron
Jingjing Qing*1, Simon Lekakh2, Mingzhi Xu1, Daniel Field3,

Georgia Southern University, PO Box 7991, Statesboro, GA 30460, US1

Missouri University of Science & Technology, 1400 North Bishop, Rolla, MO 65409, US2

U.S. Army Combat Capabilities Development Command Army Research Laboratory, 6300
Rodman Rd., Aberdeen Proving Ground, MD 21005, US3

Abstract

The complex nature of nodular graphite nuclei was studied in a partially solidified and quenched
spheroidal graphite iron (SGI) that contained small graphite nodules. The reduced graphite to
nuclei diameter ratio obtained by the accelerated solidification process increased the probability
of nuclei exposure during metallographic cross sectioning. Ten thousand graphite nodules were
analyzed to identify nucleation sites using an automated scanning electron microscopy-energy
dispersive X-ray (SEM-EDX) system and the resultant ternary plot presents a chemistry of
oxides, sulfides and nitrides located inside the graphite nodules. Focused ion beam milling was
used to extract thin foil specimens and extensive high-resolution transmission electron
microscopy (TEM) analysis of several representative nuclei was conducted. The nucleus of a
graphite nodule was composed of a Mg-O core with Mg-Ca-S and Mg-Al-Si-N compounds
attached on its sides. The crystallographic orientation relationships between different nucleating
compounds and between graphite and nucleating compounds were analyzed using selected area
diffraction patterns. For the first time, the direct observation of the nuclei interfaces revealed the
presence of nano-structured boundary layers. The formation of a complex nodular graphite
nucleus was thermodynamically simulated and the nucleation behavior of the complex
compound was linked to the novel experimental results.

Keywords: graphite, cast iron, nucleation, high resolution electron microscopy, thermodynamics

1. Introduction
Each graphite nodule in spheroidal graphite iron (SGI) needs to be nucleated during
solidification, and effective melt inoculation is vital to obtain the desired microstructure. It is

1
*Corresponding author. E-mail: jqing@georgiasouthern.edu (Jingjing Qing)
widely accepted that the spherical graphite nodules in SGI nucleate on heterogeneous sites that
exist in the molten metal during solidification. A review of the development in this area was
recently published by Stefanescu et al. [1]. However, the mechanism of these nucleating
particles’ formation, and their effect on the solidification kinetics, and shape of the graphite are
still under debate. The corresponding hypotheses and discussions in the literature are often
conflicting. With the advancement of high-resolution characterization techniques, the once
hidden nature of these fine scale nuclei are being identified and reported.

Initially, optical characterization was utilized to identify the heterogeneous nuclei inside graphite
nodules. Advancements in characterization techniques allowed for scanning electron microscopy
(SEM) and transmission electron microscopy (TEM) to reveal the complex nature of the various
compounds in the nuclei [2-8]. Skaland et al. [5] conducted a series of experiments and found
that the morphology of the spheroidal graphite nuclei was dependent on the type of inoculant
used. The observed nuclei were characterized into three categories based on shape and
composition: (i) hexagonal shaped nuclei containing Mg, Ca, and Si oxides on a sulfide core, (ii)
cuboidal shaped nuclei containing Mg and Si, and lastly (iii) irregular shaped nuclei containing
Mg and P. Riposan et al. [6] notes that the first compound formed within the graphite nuclei of
SGI is a sulfide, followed by the precipitation of a complex silicate with the graphite nucleated
on the outer silicate layer. Solberg and Onsoien [7], using the TEM diffraction, identified
complex nitrides inside the graphite nodules. The crystallography of the nitride in the graphite
nuclei was characterized as hexagonal with a trigonal superstructure, and it was suggested that
the elemental formula of the nitride was AlMg2.5Si2.5N6 with only 1-3% difference from the
lattice parameters from AlN.

Sulfur content of the initial melt influences the morphology of the SGI graphite nuclei. Nakae
and Igarashi [8] carefully controlled the sulfur content of different SGI castings and they
observed that the graphite nuclei within the SGI castings with low sulfur content (< 0.0022
wt.%) are primarily cuboidal shaped Mg-Al-Si-N. These results are consistent with the Solberg
and Onsoien observation [7]. When the sulfur content is > 0.005 wt.%, the graphite nuclei were
primarily spherical Mg-S [8]. They also showed several SEM images of sectioned graphite
nodules with complex nuclei containing MgO and MgS with the decoration of Mg-Al-Si-N. High

2
sulfur containing cast irons only provide nuclei made of faceted sulfides and MgO but the
graphite morphology also will transition to the flake morphology as the sulfur content increases.
A complex Mg-Al-Si-N has also been observed in SGI graphite nuclei from several studies [9-
12]. Stefanescu et al. [9-10] and Alonso et al. [11] showed that the nitride-type nuclei is related
to the Ti content in the iron. Low Ti (<0.014 wt.%) irons contain mainly Mg-Al-Si-N and Mg-Ca-
S in graphite nuclei, conversely the graphite nuclei in higher Ti (0.037 wt.%) SGI were cuboidal
Ti(CN) that formed on MgS. In other works [11-13], energy dispersive X-ray (EDX)
spectroscopy and TEM analyses showed that the nuclei of graphite nodules contained Al-Mg-Si-
N, MgS and Ti(CN) as well as Fe-ferrite. Crystallography analysis of the nitrides, oxides, and
sulfides were also performed in some studies [7,14] and they found the nitride is a hexagonal
crystal and oxides and sulfides are cubic crystals.

The aforementioned studies provided important information about select nuclei within graphite
nodules. However, these studies were limited in the number of particles investigated. To obtain
significant statistics the nuclei families on polished sections of SGI were investigated, and a
large population set (NUMBER) was investigated using an automated SEM-EDX(energy
dispersive X-ray) system [13]. Ternary element diagrams were used to present the chemistry of
the compounds found within the graphite nodules. The average composition of the complex
precipitates indicated that they were a mixture of oxides, sulfides and nitrides. These non-
metallic precipitates were also reproduced using transient and equilibrium thermodynamic
calculations of the chemical reactions that occur between impurities in the molten metal and the
active elements introduced by the addition of a nodulizer and inoculant [13,15]. It was shown
that nitride and sulfide particles precipitate continuously during liquid metal cooling due to the
changing chemical affinity as the temperature decreases. This is further exacerbated as the liquid
composition is enriched in segregating elements during solidification. These nitride and sulfide
particles also can promote further nucleation of graphite particles. However, it was noted by the
authors, that the SEM resolution used was insufficient and these predictions needed to be
corroborated by high resolution TEM investigations.

From this review it is noted that analysis of the complex composition of graphite nuclei has been
conducted with great detail; however, the actual nucleation behavior of different compounds are

3
not defined. Planar disregistry [7,16-17] is often used to predict nuclei effectiveness during
solidification of cast irons. Ng et al. [17] suggested that sulfide containing La could act as a
heterogeneous site for graphite because the calculated planar disregistry with graphite is only
1.4%. It should be noted that, the analysis of actual heterogeneous nuclei (oxides, sulfides, and
nitrides of Mg, Si, Ca, Ti, Ce, and La) found inside graphite nodules, did not always satisfy the
principle of crystallographic similarity between the nuclei and the graphite [8,18]. Therefore, the
author suggested using an indirect qualitative method by analyzing the data obtained from
automated SEM/EDX analysis of large population of inclusions [19]. This method determines
the nucleation activities of different precipitates by an experimentally defined averaged ratio of
element distributions between particles located within graphite nodules as well as inside the
metal matrix.

Nucleation of graphite has been shown to occur at interfaces between the nuclei and the growing
graphite nodule within several atomic layers. Non-equilibrium conditions during melt
inoculation and solidification can significantly affect these interfaces. Loper [20] discussed the
nature of FeSi inoculation considering its dissolution in the molten metal. The dissolution of
FeSi in a cast iron melt results in the formation of regions surrounding the FeSi particle where
substantial undercooling exists, with respect to the formation of graphite. High local silicon
concentrations around dissolving inoculant particles could also promote the formation of non-
equilibrium activated layers on inclusion particles existing in the molten metal; but, there is not
sufficient information about the actual interfaces between the nuclei and graphite nodules. This
information would be vital towards improving inoculation efficiency because these interfaces are
considered responsible for the actual nucleation activity. Modern high-resolution
characterization techniques should be capable to clearly display the atomic structure and reveal
the interfaces between various compounds formed within the nuclei as well as interfaces between
graphite and the nucleating particles. These advancements will facilitate the understanding of
heterogeneous nucleation of graphite. The objective of the present study is to provide insight into
various compounds in the nuclei of spheroidal graphite (SG) as well as different interfaces at
graphite nucleation sites, in order to advance the understanding of the nucleation process of
graphite in SGI, based on the experimental observations combined with thermodynamic
simulations.

4
 2. Experimental
Nuclei are located in the core of graphite nodules and thus direct observation of the nuclei is only
possible after sectioning through the center of the graphite nodule. The probability to reveal a
micrometer sized graphite nuclei located within a graphite nodule, ten times larger, significantly
increases as the graphite nodule diameter is reduced. Therefore, to reduce the nodule diameter,
the SGI specimens were produced by the interrupted solidification method as described in
previous works [20-21]. In brief, the SGI was melted in a 200-lb induction furnace from high
purity charge materials with S < 0.01 wt.%. The melt was treated in the ladle by a commercial
Fe-Si-Mg nodulizer (addition rate:1.6 wt.%) with Ce and La and FeSi base inoculant (addition
rate: 0.5 wt.%). The composition of nodulizer and inoculant are given in Table. 1. The
composition of the cast iron is shown in Table 2 and it is noted to be slightly hypereutectic,
defined by a carbon equivalent (CE=C + 0.33 Si) > 4.3 wt.%. Two minutes after the liquid metal
was treated, the SGI sample was taken.

Table 1. Composition (wt.%) of nodulizer and inoculant used to treat SGI.

Si Al Mg La Ca
Nodulizer 44.6 0.57 6.13 0.49 1.01
Inoculant 72.3 4.14 - - 0.95

Table 2. Final composition (wt.%) of the SGI. C and S are from LECO combustion and other
elements are from spectral analysis.
C S Si Mn Mg Cu Al Cr Ni Ti Fe CE
3.67 0.0072 2.32 0.3 0.045 0.6 0.03 0.05 0.04 0.006 Balance 4.44

The molten iron was extracted using quartz tubes with K-type thermocouples installed to monitor
temperature. The cooling of the iron was monitored and controlled, and the specimens were
quenched at different stages of solidification. Fig. 1(a) shows the cooling curve of an
uninterrupted baseline test without quenching (solid line) and an arrow is used to indicate the
point at which a sample was quenched (dotted line) interrupting the solidification. The graphite
nodules were retained at their early stage of growth in this quenched iron [21]. Fig. 1(b) is an
optical micrograph of the quenched iron with the graphite nodules (black spheroids)

5
approximately 5-12 μm in diameter. Fig.1(c) is the micrograph of the quenched iron after etching
with 1% Nital: the graphite nodules are the black particles; the austenite dendrites are the darker
brown dendrite feature; and the remaining phase is the remnant liquid which became the
ledeburite structure upon quenching.

(a) (b)

(c)
Fig. 1. Cooling curves of not interrupt solidified (solid line) and quenched iron (dotted line)
with the arrow indicating interrupted solidification by quenching (a) and the optical
micrograph of the quenched magnesium-treated SGI used in this study (graphite nodules are
black phase) (b). (c) is the etched micrograph of the quenched SGI.

Automated SEM/EDX analysis was performed with an ASPEX system to detect a family of
particles located inside the graphite nodules using the technique described in [19]. Over 10,000
graphite nodules were analyzed. The internal particles were detected in the core of approximately
20% of the identified graphite nodules. These internal precipitates were considered as the nuclei
of the graphite. A set of conjoined ternary diagrams were used to present the primary elemental

6
components of these precipitates. The spatial resolution of this method was approximately 1 µm
and the analysis was performed over a large number of nodules, thus the obtained data represents
statistically valid averaged results of nuclei chemistry within the SGI graphite nodules.

A TEM study was performed to obtain detailed data about nuclei chemistry, structure, and
boundaries in the graphite nodule. TEM samples were obtained from the quenched iron (Fig. 1)
and cross-sections of the nuclei inside the graphite nodules. Two TEM samples (named as A and
B) were prepared using a focused ion beam (FIB) FEI Helios NanoLab 600 Dual Beam system.
The FIB was operated at 30 kV acceleration voltage and various emission current ranging from
28 nA to 6.5 nA. The TEM utilized to study the detailed structure in the nuclei was a FEI Tecnai
F20 TEM system operated at an acceleration voltage of 200 kV. EDX mapping was conducted
using an Oxford X-Stream lithium drifted silicon detector. TEM selected area diffraction pattern
(SADP) was employed to study the crystallographic structure of the compounds in the nodular
graphite nuclei.

3. Results
3.1 Statistical Analysis of the Graphite Nuclei with Automated SEM/EDX
The precipitates found within the graphite nodules are considered graphite nuclei. Elemental
ternary diagrams of these precipitates are shown in Fig. 2. Complex Mg-Ca-La-S/Mg-Ca-La-S-
O, Mg-Al-Si-N, and Mg-Ca-Al-O were the three dominant precipitate classes. The automated
SEM/EDX analysis provided statistics of the large population of nuclei families; however,
spatial resolution of the system is limited to 1 μm and not adequate to characterize individual
submicron structural units. As such the data in Fig. 2 only presents the averaged EDX results of
the nuclei.

Fig. 2. Ternary diagrams of active elements found in nuclei of graphite nodules.

7
3.2 Detailed analysis of complex nuclei with TEM
Two particles (nucleus A and nucleus B) located in the center of different graphite nodules were
chosen for detailed characterization. A low magnification SEM image and a brightfield image at
higher magnification of nucleus A are shown in Fig. 3 that displays the complex structure of the
nuclei. Nucleus A is composed of a round central particle and four distinct radially attached
particles. Two of the particles on the right-hand side, of the micrograph shown in Fig. 3(b), are
faceted. The one on the lower left is semi-circular, and the one in the upper left region (labelled
as “U”) is irregular in shape. Elemental distributions in the different features of nucleus A are
shown in Fig. 4 and TEM diffraction results are shown in Fig. 5. Unfortunately, the zone labeled
“U” in Fig. 3(b) was too thin to produce a diffraction pattern and was quickly damaged after
exposure to the electron beam, so it was excluded from the analysis. From these results it was
found that the core of the nucleus is a MgO with a face center cubic structure and lattice
parameter of a = 0.426 nm. The upper and lower right hand particles attached to the MgO core
are faceted Mg-Al-Si-N crystals with a hexagonal structure and lattice parameters determined as:
a = 0.317 nm and c = 0.504 nm. The lower left particle attached to the MgO core is a Mg-Ca-S
with a face centered cubic structure and lattice parameter determined as a = 0.539 nm. There are
also visible nano-scale interface features (highlighted with arrows in Fig. 3(b)), which will be
discussed further in the next section.

(a) (b)
Fig. 3. Secondary electron image of the nucleus A in a graphite nodule (a) and bright field TEM
image of the complex compounds in the nucleus (b).

8
 Fig. 4. EDX mapping of the nucleus A and adjacent graphite.

(a) (b) (c)

Fig. 5. Selected area diffraction patterns of nucleus A: core - MgO along its [001] zone axes (a),
Mg-Al-Si-N along its [11̅00] zone axes (b), and Ca-Mg-S along its [101] zone axes (c).

A similar analysis was performed on nucleus B. SEM images of the FIB lift-out and TEM
brightfield images are shown in Figure 6(a) and (b) respectively. EDX analysis of the nucleus is
shown in Fig. 7 and was found to include a faceted Mg-Al-Si-N and a round Ca-Mg-S sulfide.
The composition and shape of these compounds were similar to that found in nucleus A. Also, an
interface band next to the round Ca-Mg-S particle was observed.

9
 (a) (b)
Fig. 6. Nucleus B: secondary electron image of the nucleus in graphite nodule (a) and TEM
bright field image of the complex compounds in the nucleus (b).

Fig.7. Nucleus B: EDX elemental mapping results of the nucleus and the adjacent graphite.

3.3 TEM analysis of interfaces

The orientation relationship between the MgO core and the co-precipitated Mg-Al-Si-N in
nucleus A was investigated using SADP (Fig. 8) and the results are presented in Table 3. Fig.
9(a) and Fig. 9(b) are high-resolution TEM images of the Mg-Al-Si-N and the MgO core,
respectively. Fig. 9(c) shows the semi-coherent interface between Al-Mg-Si-N and MgO.

10
 Table 3. Orientation relationship between MgO and Mg-Al-Si-N in the graphite nucleus.
Orientation Relationship MgO Mg-Al-Si-N
(111), d=0.247 nm (0002), d=0.253 nm
Parallel planes with d-spacing
(220), d=0.151 nm (21̅1̅0), d=0.158 nm
[112] [011̅0]
Parallel directions
[101] [21̅1̅0]

(a) (b)
Fig. 8. Selected area diffraction patterns for the MgO core and Mg-Al-Si-N in nucleus A:
electron beam is parallel to the [112] zone axis of MgO and [011̅0] zone axis of the Mg-Al-Si-N
(a) and electron beam is parallel to the [101] zone axis of MgO and [21̅1
̅ 0] zone axis of the Mg-
Al-Si-N (b).

Fig. 10 are the high resolution TEM images showing the interface between the Mg-Al-Si-N (left)
and the graphite (right) within the nucleus A. The nitride is differentiated as the phase with an
ordered lattice structure, while the graphite lattice shows evidence of wavy graphite basal planes.
It is found that the (101̅0) planes of the nitride (traced by dotted line in Fig. 10) (d-spacing of
0.274 nm) are parallel to the graphite basal planes (d-spacing of 0.350-0.410 nm). Semi-
coherent atomic interfaces between these phases are visible. Near this interface, the graphite
lattice is heavily distorted due to the mismatch between the two phases, and this is manifested by
wavy basal planes due to the high density of defects to accommodate the strain.

11
 (a) (b) (c)
Fig. 9. High-resolution TEM images of the Mg-Al-Si-N (a), MgO core (b), and interface between
these two compounds (c) in nucleus A. Beam direction is parallel to [101] zone axis of MgO and
[21̅1̅0] zone axis of Mg-Al-Si-N.

(a) (b)
Fig. 10. High-resolution TEM images of the Mg-Al-Si-N and graphite interfaces(a)-(b). The zone
axis of the graphite is not well-defined because of the high curvature in the graphite. Dotted
lines indicate parallel planes of the two phases.

The earlier identified curly interface with nano-sized structures were identified to be Ca-Mg-O-S
containing La in some cases. These layers coat the Ca-Mg-S faceted particles and they also
protrude into the graphite nodule. Such compounds were also located partially around the Mg-Al-
Si-N. Fig. 11(a) is a STEM image showing the location of the interface bands/layers (highlighted

12
by arrows) around the Ca-Mg-S and Mg-Al-Si-N in nucleus A, as well as in the graphite. The
nanocrystals can be clearly seen in the dark field TEM image, as shown in Fig. 11(b), and these
nanocrystal bands are also found to follow the graphite basal plane curvature, as shown in Fig.
11(a). It should be noted that the semi-circular Ca-Mg-S particle growing on the MgO also
contains nano–substructures. In the high-resolution TEM image shown in Fig. 12, it is clearly
observed that there exists a nano-sized substructure in the sulfide due to the appearance of lattice
defects (highlighted with arrows). Furthermore, the crystallographic orientation of these nano-
substructures in the Ca-Mg-S particle is well defined, from Fig. 5(c).

(a) (b)
Fig. 11. STEM image (a) and TEM dark field image (b) of the nucleus A with bands of
nanocrystals highlighted with arrows.

Analysis of nucleus B yields similar results with nucleus A. The interface bands comprised of
nanocrystals were found in nucleus B coating the semi-circular Ca-Mg-S particle for most part.
There is a location where the graphite is in direct contact with the Ca-Mg-S particle. The
interfaces between the graphite and the Ca-Mg-S is shown in Fig. 13. Graphite basal plane
spacing measured from Fig. 13 is ~0.35-0.41 nm. The (110) planar spacing of the Ca-Mg-S is
0.38 nm based on its SADP. It is evident in Fig. 13 that the Ca-Mg-S (110) planes are parallel to
the graphite (0002) basal planes. It can be seen that graphite lattice contains high a density of
defects near the interface and curvatures exist within the basal planes.

13
 Fig. 12. High resolution TEM images showing the lattice of Ca-Mg-S particle with nano-sized
substructure (highlighted area as an example) and crystallographic defects (indicated by
arrows).

An EDX line scan across the graphite-nanocrystal interface of nucleus B is shown in Fig. 14.
Changes in the diffraction contrast identifies the different layers/bands of nanocrystals from the
graphite and the Ca-Mg-S, as in Fig. 14(a). It can be seen that the nano-crystalline bands inside
the graphite particle are rich in oxygen and sulfur and contain Mg, Ca and some C. The high
resolution TEM study clearly shows that the bands found inside the graphite as well as the
partially coated surface of the Ca-Mg-S are nano-sized crystals. Fig. 15(a) is a HRTEM image of
the nanocrystal band between the graphite and the Ca-Mg-S and Fig. 15(b) shows an image of
the nano-sized crystal within the examined graphite nodule. Diffraction contrast was used to
distinguish the band from the graphite and the sulfide. The diffraction rings in the SADP
illustrates the random orientations of the nano-particles (Fig. 15(c)). The high intensity
diffraction rings correspond to interplanar spacings of 0.297 nm, 0.220 nm, 0.211 nm and 0.154
nm. These values don’t match with the interplanar spacings (d-spacing) of cubic Ca-Mg-S or
cubic MgO. Moreover, the ratios between the interplanar spacings determined using Fig. 15(c)
do not match any cubic system. The EDX results in Fig. 14 indicate its complex chemistry and
also the presence of carbon in the nanocrystals is noted.

14
 Fig. 13. High resolution TEM image of the interface between graphite and Ca-Mg-S in nucleus
B. Beam direction is parallel to the <111> zone of Ca-Mg-S. The basal plane interplanar
spacing measured ranges from 0.35 to 0.41 nm.

(a) (b)
Fig. 14. Nucleus B: STEM bright field image of nanocrystal bands in graphite (left arrow) and
coating the Ca-Mg-S (right arrow) (a) and EDX scan results across the line in (a) (b).

4. Discussion
4.1 Thermodynamic prediction
Different types of heterogeneous sites for nodular graphite nucleation may be formed during
liquid metal processing and these precipitates could be potential sites for heterogeneous
nucleation during following solidification. These nuclei can be formed by chemical reactions
between the chemically active additions, in either the nodulizer or the inoculant, and dissolved
impurities within the molten metal. TEM observation in this work show a complex SG nuclei

15
structure, indicating that it was formed through multiple precipitation steps. These steps are
potentially related to the sequence of operations used to process the liquid metal to produce SGI.
Thermodynamic simulations using free energy minimization is widely utilized for the prediction
of non-metallic inclusions particles [22]. These simulations assume that the chemical reactions in
the molten metal proceed quickly, and that the reaction rate is not a limiting step. In this study,
FactSageTM7.3, using the FS-Stel database [23] was utilized to calculate the composition of the
equilibrium compounds. The simulation software modeled the compounds formed in the molten
metal assuming 100 ppm [O] and 80 ppm [N] at 1500 °C during the nodulizing treatment with
1.6 wt.% nodulizer (Table 1) addition, assuming full recovery of the added active elements. The
reaction products formed at this stage, MgO, CaS and LaS, will be referred to as “primary”
precipitates. Irreversible reactions were assumed and reaction products were extracted from the
system after each simulation step.

Multiple meta-stable precipitates could form during the dissolution of the complex FeSi-based
inoculant (see Table 1 for detailed composition). Two effects are expected from the inoculant
dissolution: first a decreasing in the local temperature and second an increased C activity (C
saturation) due to a high local Si concentration from the addition of the inoculant. With these
conditions, several meta-stable precipitates could be formed [24-25]. The nature of these meta-
stable precipitates are not well known and the relatively short inverse effect of holding time
(typically 10-20 min) on inoculation efficiency, known as inoculation decay, supports this
hypothesis about the existence of meta-stable precipitates. The formation of these meta-stable
particles during the inoculant dissolution in liquid could play an important role in the nucleation
of graphite nodules in SGI solidified right after inoculation. However, due to their transient
nature, the dissolution of these particles during melt holding eliminates the inoculation effect.
Furthermore, it is a well-known foundry practice, that late inoculation (“in-steam” and “in-the
mold”) during mold pouring exhibits improved efficiencies supporting the hypothesis of meta-
stable precipitates.

The formation of meta-stable precipitates during dissolution of the inoculant was analyzed in this
article using step-wise simulations of local equilibrium reactions. The first step of the simulation
involved combining a portion of the initial melt at 1380oC with the inoculant at a 1:1 ratio by

16
weight. The local equilibrium was established and the reaction products were partitioned from
the liquid solution assuming a non-reversible reaction. The remaining untreated molten metal
was reintroduced to the equilibrated solution from the previous step and the extended local
equilibrium was re-calculated. This process was repeated iteratively until complete mixing was
obtained.

(a)

(b) (c)
Fig. 15. High resolution TEM image of the interfaces in Nucleus B: nanocrystal band between
the graphite and the Ca-Mg-S (a), nanocrystals in graphite (b), and the selected area diffraction
pattern of the nanocrystals between the graphite and the Ca-Mg-S (c).

17
A second stage of particle precipitations could also occur during cooling from inoculation
temperature (1380°C) to the liquids, as well as during solidification. Formation of these
secondary stable precipitates could be linked to: increasing chemical affinity of N, S, and O with
Mg and rare earth (RE) elements dissolved in the melt at decreasing temperatures and
solidification segregation. The formation of these secondary precipitates was simulated in
several steps below the liquidus temperature during solidification, progressing 10% for each step
up to 50% solid phase.

The precipitates formed during the various SGI processing steps, nodulizing, inoculation, and
solidification are shown in Fig. 16. The simulations predict the formation of primary MgO, CaS
and LaS directly in the liquid metal during the nodulizing treatment at high temperatures
(1500oC). At low sulfur contents in the initial melt (Table 2), Mg added during nodulizing works
as de-oxidizer, forming MgO. The Ca and La from the nodulizer are more effective
desulfurizing agents as illustrated by the formation of CaS and LaS. Additional simulation also
showed that MgS could be formed during nodulizing treatment of the melt with an elevated
sulfur content (S > 0.007%). The results of this simulation is consistent with the experimentally
observed composition of the complex nuclei (Fig. 3 and Fig. 4). The main primary precipitate is
shown to be a MgO which is as the core of the spherical graphite complex nuclei.

A melt inoculation temperature of 1380oC was used in this simulation, and is consistent to
industrial practice. During the dissolution of inoculation, different meta-stable carbon containing
compounds are formed in the high Si concentration zones around the dissolved FeSi based
inoculant. The identified interface layers (Fig. 11 and Fig. 14) are possibly a result of these meta-
stable reactions during inoculant dissolution, and this is corroborated by the increase in measured
carbon within these interface bands. In addition, during melt cooling to near the liquids
temperature (1180oC), during solidification, a complex nitride as well as additional sulfides are
calculated to form. It needs to be noted that only pure compounds (not solid solutions) were
simulated because of the limitations of the data-base. However, it would be anticipated that in
the actual process the formations of complex carbides, oxides and oxy-sulfides are more
probable. In addition, these simulations were done considering low concentration of trace
elements in the melt since technically pure charge materials with low trace level of elements

18
were used in this study (Table 2). However, in industrial cast irons, low concentrations of Ti or
Zr could form nitrides and change the precipitation sequence [26-27].

1.E-01
MgN
CaC2
Graphite
LaS
Precipitates, wt.%

1.E-02 CaS
MgO

1.E-03

1.E-04
Nodulizer Inoculant Solidification

Fig. 16. Simulated precipitates formed in the SGI melt (S<0.007%) after nodularizing, during
inoculation and solidification.

The simulated sequence of complex nuclei formation was supported by the observed nucleus
structure and the sequence is shown overlayed schematically on the investigated nucleus A in
Fig. 17. It could be assumed that these secondary precipitates, the nitride and sulfide, formed on
the primary oxide nucleus by multi-step co-precipitation mechanism.

Fig. 17. Steps to form of complex nuclei during SGI processing.

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4.2 Crystallography of compounds and interfaces

4.2.1 Internal structure of complex nuclei. The precipitation of the complex nuclei results from
the reactions in a multiple process steps. Additions of nodulizer in the liquid iron during Mg-
treatment led to the formation of MgO, at the core of the complex nuclei. This oxide could be
formed from a homogeneous nucleation mechanism because of the large chemical super-
saturation making the process spontaneous, and this is corroborated by the fact that there was no
internal precipitate found inside the MgO core. The total oxygen content does not change
significantly during nodulization treatment, and it is assumed that de-oxidation mainly occurred
from the Mg addition. However, this would be true only for a close system. The melt is exposed
to air during pouring, and this provides a means for oxygen re-absorption facilitating the
formation of additional MgO. The change in the precipitate families as a results of melt oxidation
during holding and mold pouring can be also predicted by thermodynamic simulations [19].
Additionally, sulfides can be formed by heterogeneous nucleation on the MgO core during
nodulization treatment or later during inoculation and liquid metal cooling, because of increasing
affinity of active elements with sulfur at decreased temperatures (Fig. 16). Ca-Mg-S of a similar
crystal structure with MgO also grew on the MgO nuclei. This sulfide particle had a nanoscale
substructure but with well-defined orientations.

Decreasing temperature will saturate the liquid metal with nitrogen and as shown from the
thermodynamic modeling the nitrides became stable near the liquidus temperature (Fig. 16). The
Mg-Al-Si-N’s crystal structure has been characterized by previous work [7]. It was noted from
reference [7] that the nitride had a hexagonal structure similar to the AlN with a hexagonal
structure. These two compounds have very similar lattice constants with only a 1-3% difference.
Growth of the observed nitride on the MgO just before solidification is crystallographically
favored due to low lattice mis-match between the two compounds, and this is also shown in the
experimental results presented in Fig. 8 and Fig. 9.

4.2.2 External interfaces between complex nuclei and graphite. In the present work the
interface between the complex nuclei and the graphite, which could be considered as nucleation
surfaces, were formed by (i) complex Mg-Al-Si-N, (ii) complex Ca-Mg-S, and (iii) the
nanocrystal band (Fig. 17). The interfaces between these compounds and the graphite will be
expounded upon as follows.

20
 (i) Complex Mg-Al-Si-N

As was observed in Fig. 10. The {101̅0} planes of the nitride are parallel to the basal plane of
the graphite, and there is a ~28% mismatch between the interplanar spacings (0.274 nm of nitride
and 0.38 nm of graphite in average). Several studies [8-12] postulated that graphite nucleation
was assisted by a Mg-Al-Si-N. The work of Solberg and Onsøien [7] indicated that the growth of
graphite on Mg-Al-Si-N was not epitaxial.

(ii) Complex Ca-Mg-S

The observed (110) interplanar spacing of the Ca-Mg-S was 0.38 nm and the (0002) interplanar
spacing of graphite varied from 0.35 to 0.41 nm (0.38 nm average). This variation in d-spacing
was due to the noted curvature of the basal planes in the graphite near nuclei. Fig. 13 clearly
indicates that the {110} planes of the sulfide are parallel to the graphite basal planes, however,
there is some noted mismatch. These results are also supported by the study conducted by Nakae
and Igarashi [8] claiming that sulfides are the best compound to nucleate graphite. However, as
noted in this work the interplanar spacing of the bulk Ca-Mg-S structure has a measureable
mismatch (~8%) with the basal planes of the graphite. Due to this mismatch, the graphite lattice
is distorted and exhibits a degree of curvature.

(iii) Nano-crystalline bands

The surface of the Ca-Mg-S particle was mostly coated by a band of nanocrystals that were
randomly oriented. These nano-bands potentially play a significant role in graphite
heterogeneous nucleation. The complicated chemistry of these nano-crystals indicates that they
are complex compound containing Mg, Ca, O, S and C. Analysis of SADP of nano-crystals (Fig.
15c) indicates that they are not simple oxides or sulfides with high symmetry crystal structure.
The crystal structure of these nanocrystals needs further investigations and CaC2 is one of the
possible compounds, because the monoclinic CaC2 d-spacings (0.293 nm, 0.217 nm, 0.208 nm,
0.156 nm [28]) match well with the high intensity rings in Fig. 15(c) (high intensity rings have d-
spacings of 0.297 nm, 0.220 nm, 0.211 nm and 0.154 nm). The reported d-spacings of the (002),
(200) and (110) planes for monoclinic CaC2 are 0.355 nm, 0.342nm and 0.334 nm, respectively
[28]. These values are close to the measured graphite basal plane spacing, which makes the CaC2
a potential candidate to nucleate the graphite and as being the interface phase. Indexing of the

21
nano-crystalline bands shown in Fig. 15(c) was challenging, and requires further investigation.
The randomly oriented nanocrystals coating may assist on mismatch reduction of the first
nucleated graphite layers.

4.3 Nanocrystals Nucleation and Early Graphite Growth

To our knowledge, no previous investigation has identified the presence of nano-crystal layers
containing Ca. The nano-crystal coated complex precipitates can be the product of transient
reactions during the inoculation process. During inoculant addition, the local saturation of
various elements as well as high local carbon activity can lead to the precipitation of several
carbon and calcium containing phases on the existing primary non-metallic particles (Fig. 16).
The instability of these nanocrystals may explain the well-documented inoculation decay
(sometimes referred to as “fade”) phenomenon during liquid SGI holding after inoculation.
These nano-layers were observed primarily around Ca-Mg-S shown as lighter gray films
highlighted with arrows in Fig. 11(a).

Classic heterogeneous nucleation theory/models assume a perfectly flat substrate surface, which
is a gross oversimplification of the interface. Recent studies revealed that the heterogeneous
nucleation on substrates, in a wetting condition, is promoted by a higher surface roughness of the
substrate [29-32] like concave areas (e.g. pores, corners or pits) [31-32] . Gránásy [30] suggested
that “circular caps” can be formed on existing cubic nano-crystalline particles during
heterogeneous nucleation when the linear size of the nucleus was bigger than 32 times the
interparticle distance. The nano-crystals are postulated from this work to agglomerated around
the nuclei which increases the surface roughness generating concave regions that could enhance
the probability of heterogeneous nucleation.

In this study, the curvature of the nano-crystalline layers were observed to be parallel to the
graphite basal plane. The circumferential growth path of the graphite around the nucleus can be
traced by the nano-crystalline layers. Multiple bands found in the graphite next to the nuclei can
be evidence of nano-crystalline participation during graphite nucleation. Fig. 15 illustrates that
the nanocrystals and graphite lattice do not share a perfect match, and the distortion of the
graphite lattice leads to a curvature. The curvature observed in the graphite lattice of the nodular
graphite might be directly related to these layers of nanocrystals. Additionally, these
nanocrystals may help to reduce the mismatch between the various phases. Furthermore, it was

22
noted that the graphite and sulfide had a high degree of mismatch and this intermediate interface
could reduce the strain associated with the mismatch. Due to the scale of these nanocrystals, as
well as high orientation variations, these nanocrystals may also provide curvature
accommodation to minimize the internal stress within the graphite.

Early growth of graphite in the SGI occurs with growth around heterogeneous nuclei. The
morphology of the compounds which grow graphite will have an effect on the final morphology
of the graphite particle. As in the present study, the Ca-Mg-S particle is semi-circular, and the
Mg-Al-Si-N is faceted with a near hexagonal shape. The growing graphite covered the surface of
the compounds as a result of a minimized total interfacial energy, and the resultant graphite
particle shape will resemble the round shape of the nucleating compound. The formed interface
nano-crystals may potentially assist on reliving the lattice mismatch thus decreasing internal
stress between graphite and nuclei. In this condition, graphite basal planes will be able to form
continuous curvature without showing faceted surface morphology.

5. Conclusions

Early growth of graphite in SGI occurs around heterogeneous nuclei. These nuclei are complex
compounds, made of MgO, Mg-Ca-S and Mg-Al-Si-N. Thermodynamic simulations of the
formation of MgO and Mg-Ca-S showed that they are the results of the reaction between the
nodulizer components with oxygen and sulfur in the molten metal at the treatment temperatures.
The complex Mg-Al-Si-N are formed later near the liquidus temperature as well as during
solidification as the solubility of nitrogen decreases. Nanocrystals rich in O and S also contain C,
Mg, and Ca. These nanocrystals are the product of transition reactions during the nodulizing and
inoculation processes. The instability of these nanocrystals may explain the well-known
inoculation decay phenomenon during liquid SGI holding. Nanocrystals potentially increases the
surface roughness of the nuclei and assists in promoting heterogeneous nucleation of graphite on
the nuclei. The crystallographic orientations between graphite basal planes and various
nucleating compound were identified. The high defect density graphite basal planes generate
curvature in the graphite nodules. These findings could facilitate future study of activation
processes of heterogeneous nucleation in different alloys.

23
 Acknowledgements

The authors would like to thank Ductile Iron Society in United States to fund the preliminary
work of this study. The authors would like to acknowledge Dr. David Van Aken and Dr. Von
Richards from Missouri University of Science & Technology for their discussions and technical
supports. The authors also wish to thank Marc Harris, Seth Rummel, Joe Govro, Dr. Terrell
Webb and Mark Emmendorfer for their assistances on the quenching experiments. The FEI
Helios NanoLab 600 dual beam FIB was obtained with a Major Research Instrumentation grant
from the National Science Foundation under contract DMR-0723128 and the FEI Tecnai F20
scanning/transmission electron microscope was obtained with a Major Research Instrumentation
grant from NSF under contract DMR-0922851. Dr. Xiaoqing He is acknowledged for his help on
obtaining the STEM image.

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