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The Role of Selenium on the Formation of Spheroidal Graphite in Cast Iron

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 metals
Article
The Role of Selenium on the Formation of Spheroidal Graphite
in Cast Iron
Gorka Alonso 1, *, Doru Michael Stefanescu 2,3 , Edurne Aguado 1 and Ramon Suarez 1,4






Citation: Alonso, G.; Stefanescu,
D.M.; Aguado, E.; Suarez, R. The Role
of Selenium on the Formation of
Spheroidal Graphite in Cast Iron.
Metals 2021, 11, 1600. https://
doi.org/10.3390/met11101600
Academic Editor: Alexander McLean
Received: 7 September 2021
Accepted: 29 September 2021
Published: 9 October 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Metals 2021, 11, 1600. https://doi.org/10.3390/met11101600
1 AZTERLAN, Basque Research and Technology Alliance (BRTA), 48200 Durango, Spain;
eaguado@azterlan.es (E.A.); rsuarez@azterlan.es (R.S.)
2 Department of Materials Science Engineering, The OHIO State University, Columbus, OH 43210, USA;
stefanescu.1@osu.edu
3 Department of Engineering, The University of Alabama, Tuscaloosa, AL 35487, USA
4 Veigalan Estudio 2010 S.L.U., 48200 Durango, Spain
* Correspondence: galonso@azterlan.es; Tel.: +34-946-215-470
Abstract: Sulfur, an element that belongs to group 16 (chalcogens) of the periodic table, is an excellent
promoter of nucleation substrates for graphite in cast iron. In ductile iron, sulfur favors a higher
nodule count, which inhibits the risk of carbides and of microporosity. It is reasonable to expect that
other elements from group 16, such as selenium or tellurium, play similar roles in the nucleation
of graphite. The objective of this paper was to investigate the effect of selenium on the process
of graphite formation. Thermal analysis cups were poured to evaluate the nodule count and size
distribution. Some of the cups were not inoculated, while others were inoculated with a Ce-bearing
inoculant, or with the Ce inoculant and additions of Se. Cross-shaped castings were also poured to
quantify the microporosity regions by tomography. It appears that selenium additions modify the
number and size of graphite particles, as well as the volume of microshrinkage. Direct correlations
between these three parameters were found. Advanced Extensive Field Emission Gun Scanning
Electron Microscope (FEG-SEM) techniques were used to identify the nature of the main nucleation
compounds. Selenides, combined with Mg and rare earths, were observed to serve as nuclei for
graphite. Their presence was justified by thermodynamics calculations.
Keywords: microporosity; sulfur; selenium; inoculant; nuclei
1. Introduction
It is well known that sulfur, an element that belongs to group 16 (chalcogens), plays
a major role in the nucleation process of spheroidal graphite (SG) cast iron, usually in
combination with other active minor elements, such as aluminum, calcium, cerium, or
barium, introduced through the inoculation and/or spheroidization processes [1–4]. Many
theories support the assumption of the heterogeneous nucleation on oxy-sulfides, Mg-Ca
sulfides, or complex Mg-Ca-RE sulfides, as the main nuclei for spheroidal and compacted
graphite [5–10]. These sulfides are among the most stable nonmetallic compounds. Similar
observations were also made in gray cast irons [11,12].
A high sulfur content inhibits graphite spheroidization and increases dross formation.
Alternatively, a low S level decreases the number of graphite particles and increases
chilling. The harmful, or beneficial, effects of sulfur are related to the amount present
before magnesium treatment, directly affecting graphite shape and nodularity. A minimum
sulfur level of at least 0.005 to 0.008% is required after the spheroidization treatment to
promote suitable nuclei for graphite precipitation and to reduce the risk of carbides. In SG
irons, small amounts of iron sulfide can be added late in the process in order to achieve
this critical content without any adverse effects on graphite nodularity.
Riposan et al. [13] showed that it was possible to use controlled sulfur additions
during the postinoculation process to produce compacted graphite cast iron without
https://www.mdpi.com/journal/metals
Metals 2021, 11, 1600 2 of 13

titanium additions. Sulfur was added as granular or powdery iron pyrites (FeS2 ), producing
inconsistent results because their fine mesh size A consistent control was achieved when
briquetted iron pyrites were used. According to Suárez et al. [14,15], the late addition of
small amounts of sulfur, in the form of pyrite granules (FeS2 ) in high-silicon and high-
carbon equivalent ductile irons, resulted in higher ferrite volume fractions, as well as
larger nodule counts, promoting the formation of potent substrates for the nucleation of
graphite. However, late sulfur additions can be detrimental to graphite morphology, setting
a threshold level of about 0.006% S, with a fast degradation of nodularity for levels above
0.008% S. On the other hand, Nakae and Igarashi [16] proposed that the range from 0.010
to dwas the most desirable S content to produce SG iron castings in order to increase the
SG nodule number. These researchers argued that spherical Mg-Ca sulfides were the main
nuclei for SG, if the S content of the base melt was higher than 0.005%, while rectangular
Mg-Si Al nitrides dominated when the S content was less than 0.0022% (Table 1).

Table 1. Influence of %S in the base iron on the nuclei of SG for Mg-treated iron, adapt from [16].

%S in Base Iron Nucleus Shape dia. (µm) Main Compounds Other Compounds
0.0022 rectangular 0.5–1.0 (Mg,Si,Al) N MgS, MgO, (Ca Mg) S
0.0052 spherical 0.5–1.0 (Mg,Ca) S MgO, (Mg,Si,Al) N
0.013 spherical 0.5–1.0 (Mg,Ca) S MgO, (Mg,Si,Al) ON
0.050 spherical 1.0–2.0 (Mg,Ca) S MgO, (La,Ce,Nd) S
0.072 spherical 1.5–5.0 (Mg,Ca) S MgO, (La,Ce,Nd) S
0.083 spherical/faceted 1.5–5.0 (Mg,Ca,Mn) S MgO, (La,Ce,Nd) S

It is also expected that other elements in the periodic table from the same group, such
as selenium or tellurium, play direct roles in the nucleation of graphite. Although the
three elements belong to the same group, 16, they present important differences in terms of
density, crystal structure, melting point, thermal conductivity, and specific heat (Table 2).
Thus, it is reasonable to assume that their behavior will be different in the process of the
formation of graphite.

Table 2. Properties of some elements from group 16 of the periodic table.

Properties Sulfur Selenium Tellurium

Density (kg/m3 ) 1960 4790 6240
Structure orthorhombic hexagonal hexagonal
Melting Point (K) 388.36 494 722.66
Boling Point (K) 717.87 957.8 1261
Specific Heat (J/Kg·K) 710 320 202
Thermal Conductivity (W/k·m) 0.269 2.04 2.35

The influence of tellurium on the formation of spheroidal graphite iron will be ana-
lyzed in future papers. This study will focus solely on the role of selenium. Most domestic
selenium is produced as commercial-grade metal, averaging a minimum of 99.5% selenium,
and is available in various forms. The global consumption of selenium during 2004 was
stipulated at about 2700 metric tons, estimating the global end-use demand as follows:
glass, 35%; chemicals and pigments, 24%; metallurgy, 23%; electronics, 10%; and other
uses, 8% [17]. More than one-half of the metallurgical selenium was used as an additive
(in amounts up to 1%) in cast iron, copper, lead, and steel alloys, improving the strength,
ductility, casting, and forming properties, and even the resistance to corrosion in the case
of magnesium-manganese alloys with additions of 0.3–0.5% Se [18].
In high-alloy steel castings, Se minimizes pinhole porosity. For stainless steels, the
addition of selenium to the liquid produces selenide compounds, with some of the metallic
elements appearing as inclusions in the steel matrix and improving the machinability.
Kurka et al. [19] found Se in MnS-type inclusions that had a significant impact on their
formability. A selenium content from 0.04 to 0.08% seems to affect the character, mor-
phology, and dispersion of the nonmetallic inclusions, decreasing ductility and increasing
Metals 2021, 11, 1600 3 of 13

sensitivity to brittle fracture. Selenium compounds (selenides) are very unstable and,
therefore, are mostly formed in solid steel on the surfaces of inclusions. When the steel
solidifies, Se refines the grain structure, acting as a weak deoxidizer that contributes to bet-
ter mechanical properties. In addition, the addition of small quantities of Se into the ladle
may promote the formation of a finer and more equiaxed structure, with less directional
differences in the properties [20].
There is not much evidence in the literature about the influence of selenium in the
formation of graphite in cast irons. It is assumed that selenium is a surface-active element
and, as such, it modifies the shape of graphite particles (from tiny flakes to nodules),
which directly affects the mechanical properties. This theory was disputed by Horie [21],
who analyzed the negative effects of tellurium and selenium on the formation of SG, and
demonstrated that, by increasing the addition of both elements, the residual magnesium
content decreased, and the shape of graphite changed successively from spheroidal to
vermicular, undercooled, and then flaky.
The purpose of this article is to investigate the role of selenium on the formation of
spheroidal graphite, studying its influence on the cooling curves, nodule count, and size
distribution, as well as on the apparition of microshrinkage. The work will also address
the impact of Se on the nucleation process through the precipitation of a new type of
nonmetallic inclusions (selenides).

2. Materials and Methods

The iron was produced in a foundry in a 12-ton 7000 Kw induction furnace. The
charge materials included: 5400 kg of steel scrap (0.01% C, 0.02% Si, 0.4% Mn, 0.02% P,
0.01% S, and 0.02% Cu), and 6600 kg of returns (3.76% C, 2.45% Si, 0.22% Mn, 0.04% P,
0.005% S, 0.07% Cu, and 0.022% Ti). The silicon level was adjusted by the addition of
FeSi75 ferrosilicon (75.09% Si, 1.49% Al, and 0.77% Ca). The carbon level was corrected
with synthetic graphite (54 kg). The melt was treated by the sandwich-method with Fe-Si-
Mg alloy (45% Si, 5.5% Mg, 2% Ca, 2.28% RE) to spheroidize the graphite. The chemical
compositions of the experimental heats are presented in Table 3. In addition to the elements
listed in the table, the melt contained 0.06% Cr, 0.004% Sn, 0.006% Al, 0.010% Ce, and
0.004% La.

Table 3. Chemical compositions (% mass) of experimental cast irons.

Heat C Si P S Mg Mn Cu Ti
1 3.55 2.39 0.014 0.003 0.034 0.55 0.14 0.020
2 3.54 2.42 0.016 0.005 0.032 0.4 0.19 0.022
3 3.58 2.40 0.015 0.005 0.032 0.4 0.21 0.021

A series of standard thermal analysis (TA) cups, and cross-shaped castings (Figure 1),
were poured from the melts, some not inoculated, while others were inoculated with
a Ce-bearing inoculant (1.83% Ce, 0.95% Al, 0.91% Ca), or with the Ce inoculant with
the addition of Se. Both selenium and the inoculant were added in a 1.3 kg hand-ladle
before pouring the samples. Additions were 0.2% for Ce-inoculant (2.6 g/cup and 5 g for
cross-shaped castings), and 0.0092% for selenium (0.12 g). The selenium was added as
pure Se (99.9%). The elemental form is generally preferred for incorporation in ingots or
castings because it melts faster [20]. A recovery of 66.6% was expected, the rest being lost
by fume or slag. The TA cups were used to generate cooling curve information, as well
as for microstructure analysis and for comparison with the nucleation in the cross-shaped
castings used for the porosity measurements.
Metals 2021, 11, 1600 4 of 13
Metals 2021, 11, x FOR PEER REVIEW 4 of 14

Figure 1. Cross shaped casting layout (dimensions in mm).

The cooling curves of the TA cups were recorded by Thermolan® system (V2
Veigalan Estudio 2010, S.L.U., Durango, Spain), and the cooling rates (first derivatives o
the cooling curves) were calculated. An example of the output data is presented in Figur
2 for the noninoculated sample, and for the Ce-inoculant and the Se + Ce-inoculant. Infor
mation on undercooling, eutectic minimum temperature, recalescence, and the maximum
Figure1.1. Cross
Crossshaped
shaped castinglayout
layout (dimensionsin in mm).
Figure
cooling ratecasting
at the end of(dimensions
solidification mm).
(CRmax) were extracted from these curves. It can b
The seen that inoculation significantly increases theThermolan
maximum®coolingsystemrate. Further discussio
Thecooling
coolingcurves of the
curves of TA
the cups
TA were
cups recorded by
were recorded by Thermolan ®(V2, Veigalan
system (V2,
Estudio between
2010, theDurango,
S.L.U., correlation between thecooling
porosity and(first
CRmax will be provided later in this pa
Veigalan Estudio 2010, S.L.U.,Spain), andSpain),
Durango, the rates
and the coolingderivatives
rates (first of the cooling
derivatives of
curves) per.
werecurves)
calculated. An example ofexample
the output data is presented in Figure 2infor the
the cooling were calculated. An of the output data is presented Figure
noninoculated sample, and
2 for the noninoculated for the
sample, andCe-inoculant and the Seand
for the Ce-inoculant + Ce-inoculant. Information
the Se + Ce-inoculant. on
Infor-
undercooling, eutectic minimum temperature, recalescence, and the
mation on undercooling, eutectic minimum temperature, recalescence, and the maximummaximum cooling rate
at the end
cooling rateofat
solidification (CRmax ) were(CR
the end of solidification extracted
max) were from these from
extracted curves. It can
these be seen
curves. that
It can be
inoculation significantly increases the maximum cooling rate. Further discussion
seen that inoculation significantly increases the maximum cooling rate. Further discussion between
the correlation
between between the
the correlation porosity
between theand CRmaxand
porosity willCRbemax
provided later in this
will be provided paper.
later in this pa-
per.

(a) (b)
Figure 2. Cooling curves (a) and their first derivatives (b) from Heat 2 showing the effect of inocula-
dCooling curves (a)
tionand their first derivatives
in increasing the maximum(b) from Heat
cooling 2 showing
rate, CRmax, the effect
at the endofofinoculation in increasing the maximum
solidification.
cooling rate, CRmax, at the end of solidification.
After cooling to room temperature, the cups were sectioned and prepared (ground and
polished) for metallographic examination. A total of 10 different fields were taken for each
(a) sample in order to analyze the morphology
(b) of the spheroidal graphite by optical microscopy.
Image processing was performed by means of the Image J software to determine the nodule
count. The minimum size considered when counting graphite particles was a surface
dCooling curves (a) and their first derivatives (b) from Heat 2 showing the effect of inoculation in increasing the maximum
of 25 µm2 , which gives a diameter of 3.36 µm.
cooling rate, CRmax, at the end of solidification.
 After cooling to room temperature, the cups were sectioned and prepared (ground
and polished) for metallographic examination. A total of 10 different fields were taken for
each sample in order to analyze the morphology of the spheroidal graphite by optical
Metals 2021, 11, 1600 5 of 13
microscopy. Image processing was performed by means of the Image J software to deter-
mine the nodule count. The minimum size considered when counting graphite particles
was a surface of 25 µ m2, which gives a diameter of 3.36 µ m.
InInorder
ordertotoidentify
identifythethepossible
possiblenucleation
nucleationsites,
sites,an
anUltra
UltraPLUS
PLUSCarlCarlZeiss
ZeissSMT
SMT(ZEISS,
(ZEISS,
Thornwood,
Thornwood,NY, NY, USA)
USA) (0.8(0.8
mmmm resolution
resolutionat 30atkV)
30inkV)thein
STEM mode was
the STEM mode used,
wasinused,
combi- in
nation with an with
combination X-Max an20X-Max
Oxford20Instruments EDX detector
Oxford Instruments EDX( Oxford
detectorInstruments, Abrington,
( Oxford Instruments,
UK) with a resolution
Abrington, UK) with ofa127 eV/ mm2.of
resolution The127most mm2 . The
eV/advanced FEG-SEM techniques,
most advanced such as spec-
FEG-SEM tech-
trums,
niques, mappings, and line scans,
such as spectrums, were applied
mappings, and lineto analyze the main
scans, were elements
applied present
to analyze theinmain
the
inclusions, and to estimate the type of compounds that can act as nuclei
elements present in the inclusions, and to estimate the type of compounds that can act as for graphite.
Thefor
nuclei formation
graphite.of Se-compounds was verified by the commercial software, FactSage6.41,
whoseThe theoretical
formationbasisofis Se-compounds
the equilibrium and wasphase transformations
verified for the minimization
by the commercial software, Fact- of
Sage6.41,
the Gibbs freewhose theoretical
energy. basis iscalculation
Two different the equilibriummodules, and“Equilib”
phase transformations
and “Reaction”,for the
were
minimization
used to determine of the
the precipitation
Gibbs free energy. Twocompounds.
of possible different calculation modules,
The “Equilib” module“Equilib”
determinesand
“Reaction”,
the chemical were used toof
composition determine
compounds the when
precipitation of possible
the elements compounds.
react partially The “Equilib”
or totally to reach
amodule determines
state of chemical the chemical
equilibrium undercomposition of compounds
the chosen composition when the elements
and temperature conditions react
partially
(Figure 3).or totally
The to reach
“Reaction” a statedetermines
module of chemicalthe equilibrium
change in under the chosen
the extensive composition
thermodynamic
and temperature
properties, conditions
such as enthalpy, (Figureor3).
entropy, The “Reaction”
specific heat to simple module
speciesdetermines
or chemicalthe change
reactions.
Itinisthe
seenextensive
that MgSe thermodynamic
and La2Se2 areproperties,
stable solidssuch as enthalpy, of
at temperatures entropy,
1500 °C, or and
specific
thatheat
Ce2Cto 3
simple
forms species
at 1200 °C.or chemical
It is reasonable reactions.
to assume It isthat
seen thatcompounds
these MgSe and can La2 act
Se2 as
are stable solids at
nuclei.
temperatures of 1500 ◦ C, and that Ce2 C3 forms at 1200 ◦ C. It is reasonable to assume that
these compounds can act as nuclei.

0%S + 0.012%Se

CHEMICAL
COMPOSITION

C 3.55

Si 2.40

Mg 0.033
(%wt)

Mn 0.45

S 0

Se 0.012

Ce 0.009

La 0.003

T (°C)

Stabilityofofselenides
Figure3.3.Stability selenidesaccording
accordingtotoFactSage,
FactSage,between
between300
300and
and1500 ◦ C, assuming the initial
1500°C,
Figure assuming the initial
chemicalcomposition
chemical compositionlisted
listedininthe
thefigure.
figure.

X-raycomputer
X-ray computertomography
tomographywas wasused
usedtotoevaluate
evaluateporosity.
porosity.This
Thismethod
methodhas
hasbeen
been
proven to be accurate on SG iron samples by Borgs and Stets [22], who compared
proven to be accurate on SG iron samples by Borgs and Stets [22], who compared the the
tomography and the metallographic sections. In this work, tomographic inspection
tomography and the metallographic sections. In this work, tomographic inspection was was
performed on a YXLON equipment Mod. Y.CT Compact 450 kV and 1.5 mA (YXLON In-
performed on a YXLON equipment Mod. Y.CT Compact 450 kV and 1.5 mA (YXLON
ternational X-Ray GmbH, Hamburg, Germany). The cross-shaped castings were sectioned
International X-Ray GmbH, Hamburg, Germany). The cross-shaped castings were sec-
perpendicular to the vertical axis, and the sections were analyzed. The distance between
tioned perpendicular to the vertical axis, and the sections were analyzed. The distance
the sectioning planes was 1 mm, with a pixel size of 0.17 mm. A total of 83 sections per
sample were produced. As an example, 4 of the 83 cuts on the sample with 1.8 Ce inoculant
are shown in Figure 4.
 Metals 2021, 11, x FOR PEER REVIEW 6 of 14

Metals 2021, 11, 1600 between the sectioning planes was 1 mm, with a pixel size of 0.17 mm. A total of 83 sec-
6 of 13
tions per sample were produced. As an example, 4 of the 83 cuts on the sample with 1.8
Ce inoculant are shown in Figure 4.

Figure4.4. Example
Figure Example of
of tomography
tomographysections
sectionsfor
fora across-shaped casting
cross-shaped inoculated
casting with
inoculated Ce-inoculant;
with Ce-inoculant;
volume of internal defect: 101.82 mm3.3
volume of internal defect: 101.82 mm .
After the
After the radiation
radiation of
of the
thesample,
sample,one
onefile
fileper
perplane
planewas
wasgenerated andand
generated then rebuilt
then rebuilt
into a 3D model using VG Studio Max 2.0. By means of this software, the total volume of
into a 3D model using VG Studio Max 2.0. By means of this software, the total volume
the sample was calculated. By applying techniques based on contrast and grey levels anal-
of the sample was calculated. By applying techniques based on contrast and grey levels
ysis, the volume of defect is identified and evaluated.
analysis, the volume of defect is identified and evaluated.

3.3.Results
Results and
and Discussion
Discussion
3.1.Correlation
3.1. Correlation between
Between Cooling
Cooling Curve
CurveParameters,
Parameters,Nodule
NoduleCount
Countand Porosity
and Porosity
The experimental
The experimental results
resultsare
aresummarized
summarizedininTable
Table4. 4.
It can be be
It can seen that,
seen as expected,
that, as expected,
the nodule count increased considerably because of Ce inoculation. The Ce-Se
the nodule count increased considerably because of Ce inoculation. The Ce-Se combination combina-
tionthe
was wasmost
the most efficient,
efficient, producing
producing the highest
the highest number
number of nodules
of nodules in in
allall three
three heats.
heats.
Table 4. Experimental results showing the effect of inoculant and Se additions on formation of microshrinkage and cooling
Table 4. Experimental results showing the effect of inoculant and Se additions on formation of microshrinkage and cooling
curve parameters.
curve parameters.
Heat Inoc. Nod/mm2 TL ℃ TEmin °C ∆Trecal °C TS °C CRmax °C/s Microshrinkage mm3
1.8 Ce 255 1146.8
◦ 1141.3
◦ 5.6 ◦ 1118.6 3.80 ◦ Microshrinkage
11.22
Heat
1 Inoc. Nod/mm2 TL C TEmin C ∆Trecal C TS C◦ CRmax C/s 3
1.8 Ce + Se 377 1149 1147.4 2.9 1125 3.88 22.26mm
none
1.8 Ce 140
255 1135.9
1146.8 1134.1
1141.3 3.5
5.6 1104.6
1118.6 2.443.80 148.46 11.22
12 1.8Ce
1.8 Ce+ Se 270
377 1148.2
1149 1142.5
1147.4 5.7
2.9 1125.1
1125 - 3.88 2.8522.26
1.8 Ce + Se 333 1152.2 1144.5 7.8 1127.3 3.38 0
none 140 1135.9 1134.1 3.5 1104.6 2.44 148.46
2 none
1.8 Ce 216
270 1139.7
1148.2 1135.5
1142.5 4.1
5.7 1106.1
1125.1 2.58 - 272.822.85
3 1.8Ce
1.8 Ce+ Se 368
333 1148.5
1152.2 1141.3
1144.5 7.2
7.8 1125.4
1127.3 3.323.38 101.82 0
1.8 Ce + Se 386 1149.6 1143.1 6.5 1124.5 3.06 6.50
none 216 1139.7 1135.5 4.1 1106.1 2.58 272.82
3 1.8 Ce 368 1148.5 1141.3 7.2 1125.4 3.32 101.82
1.8 Ce + Se 386 This1149.6
improvement1143.1
in nodule count
6.5 translates,1124.5
in most cases,3.06
to an important6.50 reduc-
tion in the size of the microshrinkage. As shown in in Figures 5 and 6a, as the nodule count
increases, the amount of porosity decreases. The addition of Se appears to emphasize this
This improvement in nodule count translates, in most cases, to an important reduction
tendency, except for Heat 1, where the samples inoculated with 1.8 Ce + Se present a mi-
in the size of the microshrinkage. As shown in Figures 5 and 6a, as the nodule count
croporosity of about a factor of two more than those inoculated only with Ce. This differ-
increases, the amount of porosity decreases. The addition of Se appears to emphasize
ence can be attributed to the bad behavior of the feeder, or to a poor performance of Se.
this tendency, except for Heat 1, where the samples inoculated with 1.8 Ce + Se present
Because of the low value of sulfur in this sample (0.003% S vs. 0.005% S in the other ones),
a microporosity of about a factor of two more than those inoculated only with Ce. This
which has already been shown as an excellent promoter of potent substrates for the nu-
difference can be attributed to the bad behavior of the feeder, or to a poor performance of
cleation of graphite [5,8,10], graphite expansion may become insufficient to compensate
Se. Because of the low value of sulfur in this sample (0.003% S vs. 0.005% S in the other
the solidification shrinkage, increasing the risk of microporosity formation.
ones), which has already been shown as an excellent promoter of potent substrates for the
nucleation of graphite [5,8,10], graphite expansion may become insufficient to compensate
the solidification shrinkage, increasing the risk of microporosity formation.
 Volumen de defecto: Volumen de defecto: Volumen de defecto:
Metals 2021, 11, 1600 272.82 mm³ 101.82 mm³ 6.50 mm³ 7 of 13
Metals 2021, 11, x FOR PEER REVIEW 7 of 14
216 nod/mm 2 368 nod/mm 2 386 nod/mm 2
(a) (b) (c)

Figure 5. Evaluation of microporosity by tomography in cross-shaped castings from Heat 3: (a) non-
inoculated; (b) inoculated with Ce-inoculant; (c) inoculated with Ce-inoculant + Se.

A good correlation is also seen between the nodule count and CRmax. However, the use of
CRmax in differentiating between Ce-inoculated and (Ce + Se)-inoculated is not conclusive as
we only have one data point. Similarly, while CRmax exhibits a clear increase with inoculation
(Figure 6b), it appears to be a less precise predictor of the differences in microshrinkage be-
tween the inoculated irons (Figure 6c). This is due, at least in part, to the inaccuracies resulting
from Se assimilation in the melt during inoculation in the hand ladle. To reach a definitive
Volumen
conclusion de defecto:
on this Volumen
issue, more research de are
data defecto:
required. Volumen de defecto:
272.82 mm³ 101.82 mm³ 6.50 mm³

216 nod/mm 2 368 nod/mm 2 386 nod/mm 2

(a) (b) (c)

Figure
Figure 5. Evaluation
5. Evaluation of microporosity
of microporosity by tomography
by tomography in cross-shaped
in cross-shaped castings
castings from Heat 3:from Heat 3:
(a) non-
(a) non-inoculated; (b) inoculated with Ce-inoculant; (c) inoculated with Ce-inoculant
inoculated; (b) inoculated with Ce-inoculant; (c) inoculated with Ce-inoculant + Se. + Se.

A good correlation is also seen between the nodule count and CRmax. However, the use of
CRmax in differentiating between Ce-inoculated and (Ce + Se)-inoculated is not conclusive as
we only have one data point. Similarly, while CRmax exhibits a clear increase with inoculation
(Figure 6b), it appears to be a less precise predictor of the differences in microshrinkage be-
tween the inoculated irons (Figure 6c). This is due, at least in part, to the inaccuracies resulting
from Se assimilation in the melt during inoculation in the hand ladle. To reach a definitive
conclusion on this issue, more research data are required.

Metals 2021, 11, x FOR PEER REVIEW 8 of 14

(a) (b)

(a) (c) (b) (d)

6. Correlation
Figure 6.
Figure Correlation between
between various
various measured
measured parameters
parameters andand microshrinkage;
microshrinkage; the
the variable
variable on
on
abscise reflects
the abscise reflects the
thesequential
sequentialleft-to-right
left-to-rightchange
changenot
notinoculated-inoculated-inoculated
inoculated-inoculated-inoculated + Se:
+ Se: a)
correlation between
(a) correlation between microshrinkage
microshrinkage andandnodule
nodulecount;
count;b)(b)correlation
correlationbetween
betweennodule
nodule count
count and
cooling rate; (c)
cooling rate; c) correlation
correlation between
between microshrinkage
microshrinkage andand the
the maximum
maximum cooling
cooling rate;
rate;(d)
d) correlation
correlation
between microshrinkage and minimum eutectic temperature
between microshrinkage and minimum eutectic temperature.

Finally,
A good as shown inisFigure
correlation 6d, abetween
also seen higher TE indicates
theminnodule a lower
count microshrinkage.
and CRmax . However, the
use of CRmax in differentiating between Ce-inoculated and (Ce + Se)-inoculated is not
3.2. Size Distribution
conclusive as we only of have
Graphite
one data point. Similarly, while CRmax exhibits a clear increase
Ten images per sample were analyzed to characterize the size distribution of sphe-
roidal graphite. An example of measured graphite nodule histograms for cups with and
without inoculation (Ce-inoculant) is shown in Figure 7. The experiments indicate that the
nucleation of SG can follow a monotonic trend (only one maximum on the size distribu-
 (c) (d)

Metals 2021, 11, 1600 Figure 6. Correlation between various measured parameters and microshrinkage; the variable 8 of on
13
the abscise reflects the sequential left-to-right change not inoculated-inoculated-inoculated + Se: a)
correlation between microshrinkage and nodule count; b) correlation between nodule count and
cooling rate; c) correlation between microshrinkage and the maximum cooling rate; d) correlation
between
with microshrinkage
inoculation and
(Figure minimum
6b), eutectic
it appears temperature
to be a less precise predictor of the differences in
microshrinkage between the inoculated irons (Figure 6c). This is due, at least in part, to the
Finally, resulting
inaccuracies as shownfrom in Figure 6d, a higher
Se assimilation TEmin
in the indicates
melt duringainoculation
lower microshrinkage.
in the hand ladle.
To reach a definitive conclusion on this issue, more research data are required.
3.2. Size Distribution
Finally, as shown of Graphite
in Figure 6d, a higher TEmin indicates a lower microshrinkage.
Ten images per sample were analyzed to characterize the size distribution of sphe-
3.2. Size
roidal Distribution
graphite. of Graphite
An example of measured graphite nodule histograms for cups with and
withoutTeninoculation (Ce-inoculant)
images per sample is shown
were analyzed in Figure 7. The
to characterize experiments
the size indicate
distribution that the
of spheroidal
nucleation
graphite. An of example
SG can follow a monotonic
of measured graphitetrend (only
nodule one maximum
histograms on with
for cups the size
anddistribu-
without
tion curve) or
inoculation can exhibit several
(Ce-inoculant) nucleation
is shown in Figurewaves
7. The(several maxima).
experiments Chisamera
indicate et al.
that the [23]
nucle-
ationshown
have of SG can
that follow
complex a monotonic
FeSi inoculantstrend (only
with Ca,one maximum
Ce, S, and O extendon the size distribution
graphite nucleation
curve) orthe
through can exhibit
end several
of eutectic nucleation waves
solidification. A bimodal(several
volumemaxima). Chisameraofetgraphite
size distribution al. [23]
have shown
nodules that
(a set ofcomplex FeSi inoculants
small nodules coexistingwith
withCa,aCe,
nearS, normally
and O extend graphiteset
distributed nucleation
of large
through the
nodules) wasend of eutectic
observed solidification.
by Lekakh A bimodal
et al. [24] and suggest volume
a linksize distribution
between of graphite
the second nucle-
nodules
ation (a and
wave set of small
lower nodules coexisting
microporosity. While with
none aofnear
the TAnormally
cups indistributed
this researchset of large
produced
anodules) was observed
second nucleation wave by (two
Lekakh et al. [24]
maxima) andsize
in the suggest a link between
distribution curves, athe second
clear nucle-
difference
ation wave and lower microporosity. While none of the TA cups in this
was observed in the microstructures and distribution curves for the inoculated irons as research produced
a second nucleation
compared wave (two maxima)
with the noninoculated. in the
The lack size distribution
of inoculation curves,
produces a clear
a more difference
uniform dis-
was observed in the microstructures and distribution curves for the
tribution spread over different sizes of graphite, in addition to the bad shape parametersinoculated irons as
compared
of with
spheroidal the noninoculated.
graphite (low roundnessThe lack of inoculation
and high produces
aspect ratio), a more
and lower uniform
nodule distri-
count.
bution spread over different sizes of graphite, in addition to the bad shape parameters of
spheroidal graphite (low roundness and high aspect ratio), and lower nodule count.

30 30

25 25

20 20
graphite
graphite

15 15

10 10

5 216 nod/mm2 5 368 nod/mm2

0 0

Diameter (µm) (a) Diameter (µm) (b)

Figure 7.
Figure Unetched micrographs
7. Unetched micrographs and
and graphite
graphite size
size distribution
distribution for
for samples
samples from
from Heat
Heat 33 non
non inocu-
inocu-
lated (a) and inoculated with Ce-inoculant (b).

The addition of Se considerably modifies the size distribution of graphite, moving the
formation of graphite to the left, generating finer graphite. Indeed, as shown in Figure 8,
the addition of Ce-inoculant (1.8 Ce) produces a distribution with 55% of the nodules in
the range of a 5–20 µm diameter, vs. 66% for the sample where (Ce + Se)-inoculant was
added. This finer graphite generation, assumed to form at the end of solidification [25],
could better counteract the austenite contraction in the last stages of solidification, and may
be responsible for the decrease in the microshrinkage formation (Figure 5).

Metals 2021, 11, 1600
8, the addition of Ce-inoculant (1.8 Ce) produces a distribution with 55% of the nodules
in the range of a 5–20 µ m diameter, vs. 66% for the sample where (Ce + Se)-inoculant was
added. This finer graphite generation, assumed to form at the end of solidification [25],
could better counteract the austenite contraction in the last stages of solidification, and
may be responsible for the decrease in the microshrinkage formation (Figure 5). 9 of 13

Figure 8.
Figure Influence of
8. Influence of the
the addition
addition of
of Se
Se on
on graphite
graphite size
size distributions
distributions for
for TA
TA cups
cups from
from Heat
Heat 2.
2.
3.3. Thermodynamics Calculations
3.3. Thermodynamics Calculations
According to the previous results, it appears that selenium contributes favorably to
Metals 2021, 11, x FOR PEER REVIEW Accordingof
the formation tographite.
the previous
It isresults,
expectedit appears
that thisthat selenium
element contributes
forms different favorably
10 of to
14
nonmetallic
the formation of graphite. It is expected that
inclusions that can act as nuclei for graphite. this element forms different nonmetallic in-
clusions that can act as nuclei for graphite.
The possible precipitation and stability of these compounds was analyzed through
an Ellingham’s diagram (Figure 9) based on the calculations from the FactSage database
(V6.4, GTT Technologies, 52134, Herzogenrath, Germany). This diagram, which shows the
dependence of the stability for compounds as a function of temperature [26], reveals the
formation of several thermodynamically stable Se compounds (selenides), such as CaSe,
LaSe, and MgSe (it is somehow surprising that no Ce selenide was detected). Ca-selenides
seem to be the most stable of all the selenides. However, sulfides exhibit, in most cases,
lower standard free energy formation (∆G0). Thus, it is expected that Mg, Ca, or RE prefer
to combine with sulfur rather than with selenium. Depending on the content of Se and S,
selenides can coexist with their corresponding sulfides. In the case of Ca, for example, the
melting point for CaS is 2526 °C vs. 1408 °C for CaSe, so both can appear together if the
temperatures are not very high.

Figure9.
Figure Standardfree
9.Standard freeenergy
energy of
of formation
formation of
of some
some selected
selected sulfides
sulfides and
and selenides.
selenides.

The possible
3.4. Nature of Nucleiprecipitation and stability of these compounds was analyzed through
an Ellingham’s diagram (Figure 9) based on the calculations from the FactSage database
An exhaustive SEM analysis of the type of nonmetallic inclusions that can act as
nucleation sites for graphite shows that the main nuclei in the inoculated irons were made by
rounded sulfides and polygonal Mg-Si-Al nitrides, as is summarized in Table 5. Both types of
inclusions can appear alone (Figure 10a), or in the same graphite aggregate (Figure 10b).
Metals 2021, 11, 1600 10 of 13

(V6.4, GTT Technologies, 52134, Herzogenrath, Germany). This diagram, which shows the
dependence of the stability for compounds as a function of temperature [26], reveals the
formation of several thermodynamically stable Se compounds (selenides), such as CaSe,
LaSe, and MgSe (it is somehow surprising that no Ce selenide was detected). Ca-selenides
seem to be the most stable of all the selenides. However, sulfides exhibit, in most cases,
lower standard free energy formation (∆G0 ). Thus, it is expected that Mg, Ca, or RE prefer
to combine with sulfur rather than with selenium. Depending on the content of Se and S,
selenides can coexist with their corresponding sulfides. In the case of Ca, for example, the
melting point for CaS is 2526 ◦ C vs. 1408 ◦ C for CaSe, so both can appear together if the
temperatures are not very high.

3.4. Nature of Nuclei

An exhaustive SEM analysis of the type of nonmetallic inclusions that can act as
nucleation sites for graphite shows that the main nuclei in the inoculated irons were
made by rounded sulfides and polygonal Mg-Si-Al nitrides, as is summarized in Table 5.
Both types of inclusions can appear alone (Figure 10a), or in the same graphite aggregate
(Figure 10b).

Table 5. Main inclusions detected in the graphite acting as nuclei.

Heat Inoc. No. Nuclei Oxides Sulfides (MgSiAl) N Ti (CN) Graph. with RE Graph. with Se
1.8 Ce 20 4% 40% 33% 25% 25% 0%
1 1.8 Ce + Se 20 0% 57% 30% 13% 50% 60%
1.8 Ce 20 7% 46% 36% 11% 35% 0%
Metals22021, 11, x FOR PEER REVIEW 11 of 14
1.8 Ce + Se 20 3% 47% 29% 21% 50% 50%

Figure10.
Figure 10.Different
Differentnonmetallic
nonmetallicinclusions
inclusionsacting
actingasasnucleation
nucleationsites
sitesfor
forthe
thegraphite:
graphite:(a)(a) a complex
a complex Mg-Si-Al
Mg-Si-Al nitride;
nitride; (b)(b)
a
a combination of (MgSiAl) N + (MgCaRE) S; (c) a small Ti (CN) growing on a big Mg-Ca
combination of (MgSiAl) N + (MgCaRE) S; (c) a small Ti (CN) growing on a big Mg-Ca sulfide. sulfide.

Some oxides
Some oxides werewere also
also found.
found. TheThe formation
formation of of cubic
cubic TiTi carbides
carbides is is determined
determined by by
the content of Ti in the base melt (>0.020% Ti) [3,27,28]. They are never
the content of Ti in the base melt (>0.020% Ti) [3,27,28]. They are never found isolated andfound isolated and
need another
need another inclusion
inclusion (complex
(complex nitride
nitride or
or sulfide)
sulfide)to tonucleate
nucleate (Figure
(Figure10c).
10c).
The presence
The presence of of RE
RE isis relevant,
relevant, particularly
particularlyin insamples
sampleswithwiththethe addition
additionof ofSe,
Se, where
where
they are
they are always
always detected
detected as as sulfides
sulfides (Figure
(Figure 10b),
10b), or
or selenides
selenides (Figure
(Figure 11),
11), which
which verifies
verifies
the great
the great affinity
affinity between
between SS and and SeSe and
and RERE (mainly
(mainlyLa Laand
andCe).
Ce). Their
Their presence
presence seems
seems toto
be linked to the Mg treatment(45%Si, 5.5%Mg, 2%Ca, 2%RE) used
be linked to the Mg treatment(45%Si, 5.5%Mg, 2%Ca, 2%RE) used for the spheroidization for the spheroidization
process. The
process. The detection
detection ofof SeSe acting
acting asas aa nucleation
nucleation site
site for
for graphite
graphite ininsamples
samples inoculated
inoculated
with1.8
with 1.8 Ce
Ce ++ Se, which are characterized
characterized by by a higher nodule
nodule count,
count, is
is evident
evident (>50%
(>50% cases);
thus, the
thus, the important
important role role that
that this
this element
element plays
plays in
in the
the formation
formation of of graphite
graphite isisclear.
clear.The
The
theoretical
theoretical formation
formation of of these
these SeSe compounds
compounds was was justified
justified previously
previously by by thermodynamic
thermodynamic
calculations.
calculations.

Metals 2021, 11, 1600
process. The detection of Se acting as a nucleation site for graphite in samples inoculated
with 1.8 Ce + Se, which are characterized by a higher nodule count, is evident (>50% cases);
thus, the important role that this element plays in the formation of graphite is clear. The
theoretical formation of these Se compounds was justified previously by thermodynamic
calculations. 11 of 13

Figure11.
Figure 11. SEM
SEM images
images of
ofaagraphite
graphitenucleating
nucleatingonona selenide, and
a selenide, corresponding
and WDX/SEM
corresponding spectrums,
WDX/SEM at different
spectrums, posi-
at different
tions: position 1 − (Mg,Ca) S; position 2 − (Mg,Se,Ca,Ce,La) S.
positions: position 1 − (Mg,Ca) S; position 2 − (Mg,Se,Ca,Ce,La) S.

Theseselenides
These selenidescan
canact
actas
asdirect
directnucleation
nucleationsites
sitesfor
forgraphite
graphite(Figure
(Figure11),
11),or
oras
asnuclei
nuclei
for other nonmetallic inclusions (usually a complex of Mg-Si-Al-N). An example
for other nonmetallic inclusions (usually a complex of Mg-Si-Al-N). An example is illus- is illus-
trated in Figure 12, where an analysis, using X-ray concentration graphs, reveals
trated in Figure 12, where an analysis, using X-ray concentration graphs, reveals that Mg, that Mg,
Si, Al, and N show composition peaks at the same position. Then, S, Se, and Ca present aa
Si, Al, and N show composition peaks at the same position. Then, S, Se, and Ca present
clearcoincidental
clear coincidental maximum.
maximum. Thus,
Thus, the
the nucleus
nucleus ofof this
this graphite
graphite seems
seems toto be
beformed
formedby byaa
bigpolygonal
big
Metals 2021, 11, x FOR PEER REVIEW polygonalMg-Si-Al
Mg-Si-Alnitride
nitride(≥
(≥10 µ m) that
10 µm) that has
has nucleated
nucleated on
on two
two small
smallCa Casulfides
sulfides and
12 of and
14
selenides,demonstrating
selenides, demonstratingthethecoexistence
coexistenceof ofboth
bothcompounds,
compounds,as asdiscussed
discussedearlier.
earlier.

Figure 12. Determination of nuclei in function of X-ray concentration line scan graphs.
Figure 12. Determination of nuclei in function of X-ray concentration line scan graphs.

4. Conclusions
4. Conclusions
Correlationsbetween
Correlations betweenthe themicroshrinkage
microshrinkage (shrinkage
(shrinkage porosity)
porosity)and andsome
somemetallo-
metallo-
graphic
graphic and
and thermalanalysis
thermal analysisparameters
parameters ofof spheroidal
spheroidal graphite
graphiteirons
ironswithwith4.3%
4.3%carbon
carbon
were
were evaluated
evaluated onon thermal
thermal analysis
analysis cups
cups and
and cross-shaped
cross-shaped castingspoured
castings pouredfrom
fromananindus-
in-
dustrial
trial batch batch of Mg-treated
of Mg-treated iron.iron. A commercial
A commercial inoculant,
inoculant, richrich
in in
CeCe andand someadditions
some additionsof
of pure
pure Se, was
Se, was added added in the
in the hand-ladle
hand-ladle before
before pouringthe
pouring thesamples.
samples. The
Theinfluence
influenceofofthese
these
additions
additions onon the
the processofofthe
process theformation
formationofofgraphite
graphite waswas also
also studied.
studied.
AsAs expected,the
expected, theinoculation
inoculation process
processconsiderably
considerably improved
improved all the
all parameters of theof
the parameters
cooling curves, as well as the nodule count, drastically decreasing
the cooling curves, as well as the nodule count, drastically decreasing the apparitionthe apparition of mi-of
croporosity. It was found that the addition of selenium increases the
microporosity. It was found that the addition of selenium increases the eutectic minimum eutectic minimum
temperatureand
temperature andthethesolidus
solidus temperature,
temperature,asaswell
well as as
thethe
number
numberof nodule spheroids.
of nodule Se-
spheroids.
lenium modifies the size distribution of graphite, producing finer graphite that seems to
Selenium modifies the size distribution of graphite, producing finer graphite that seems
nucleate at the end of solidification, reducing substantially, in most cases, the volume of
microshrinkage. This behavior is explained by the formation of some Se compounds
(selenides) that can act as excellent nuclei for graphite. Thermodynamics calculations and
a complete SEM analysis supported this assertion.
Metals 2021, 11, 1600 12 of 13

to nucleate at the end of solidification, reducing substantially, in most cases, the volume
of microshrinkage. This behavior is explained by the formation of some Se compounds
(selenides) that can act as excellent nuclei for graphite. Thermodynamics calculations and
a complete SEM analysis supported this assertion.

Author Contributions: Conceptualization, G.A. and D.M.S., methodology, G.A.; software, G.A. and
E.A.; validation, D.M.S., G.A. and R.S.; formal analysis, G.A.; investigation, G.A.; resources, G.A. and
D.M.S.; data curation, G.A. and D.M.S.; writing—original draft preparation, G.A.; writing—review
and editing, D.M.S. visualization, G.A.; supervision, R.S.; project administration, R.S. All authors
have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors would like to acknowledge Diputacion Foral de Bizkaia for sup-
porting this research.
Conflicts of Interest: The authors declare no conflict of interest.

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