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Copyright 2009 American Foundry Society, www.afsinc.org. Reprinted with permission.

AFS Sponsored Research


SiCTHE MOST EFFICIENT ADDITION TO
INCREASE THE NODULE COUNT IN DUCTILE IRON
M. Popescu, R. Zavadil, and M. Sahoo
CANMET Materials Technology Laboratory, Ottawa, Ontario, Canada
Copyright 2008 American Foundry Society

Abstract
In the first phase of the AFS-sponsored research project
on Restoring Techniques for Monday Morning Iron,
the investigation focused on the extent to which prolonged
holding of the base iron in an induction furnace affected the
quality of ductile iron. The objective in Phase II was to find a
way to increase the nucleation potential of iron having a high
chilling tendency. The technique consisted of adding SiC,
SiCa, crystalline graphite, etc., to a base iron in the furnace
before the Mg-treatment with the aim to supply the iron with
active elements considered suitable sites for graphite nodule

nucleation. The results of this investigation demonstrated


that SiC is the most efficient addition to increase the iron
nucleation potential. Based on these results, tests were run
under commercial foundry operating conditions. This report
presents and discusses the results of investigation performed
in the MTL laboratory with detailed analysis of chilling
tendency, microstructure and shrinkage propensity on test
samples from both base and final ductile irons.
Keywords: ductile iron, inoculation, Monday Morning Iron,
nodule count, chill, nucleation, undercooling.

Introduction

Monday Morning syndrome and to take action to restore the


iron nucleation potential before the Mg-treatment and pouring
the pieces.

Grey and ductile iron foundries are familiar with a condition


where iron held for long periods in the furnace, after normal
processing, presents undercooled microstructures leading to
abnormal values for properties such as hardness and tensile
strength. Given that this situation is encountered where the iron
is held over the weekend, the iron presenting this condition is
called Monday Morning Iron. Since the iron is not responsive
to inoculation, another frequent name is Dead Iron. The aim
of this research was to find a solution to restore the nucleation
potential of an iron with this condition. The research was initiated
within the AFS Cast Iron Division and has been carried out in
two phases. The objectives of the first phase was to investigate
the effect of holding temperature and time on the nucleation
potential of the iron and to better understand the conditions
promoting Monday Morning Iron. The investigation was done
on both grey and ductile irons. The results of this investigation
reinforced the importance of holding temperature and time in
the furnace.1,2 The negative effect of holding on the nucleation
potential of the iron depends on the initial state of iron and is
more powerful at higher temperatures where the effect is more
obvious and takes place more rapidly if the iron initial nucleation
capability is poor and the heat is overheated. The result is the
formation of undercooled graphite and ferrite in grey iron and
lower nodule count and heterogeneous distribution in ductile
iron. The investigations in the first phase indicated that changes
in the microstructure and chilling tendency of the base iron
are reflected in the nodule count and distribution and chilling
tendency of the ductile iron. However, more data is necessary
to provide information of practical interest for a systematic
and thoroughly controlled foundry testing in ductile iron
production. This would constitute an efficient way to identify

International Journal of Metalcasting/Winter 09

The objective in Phase II was to identify in laboratory


conditions the most efficient way to increase the nucleation
potential of iron presenting increased undercooling
tendency. Two different methods were explored for this
purpose. One method was to treat the base iron with selected
metallurgical additives. Based on the data published in the
literature the following agents were selected for this study:
SiC, a mixture of SiC with FeSi5%Mg (Mixture X), a
mixture of SiC with foundry grade FeSi75% (Mixture Y),
SiCa, crystalline graphite and FeS. These additives were
considered to provide the liquid iron with active elements to
form silicate sulphides that are known to constitute suitable
sites for graphite nodule nucleation. Their effect on the
iron state was monitored and compared with the iron initial
state in both base and ductile irons. Changes in the base
iron microstructure, chilling tendency and hardness before
and after addition were investigated and the data evaluated
against the microstructure, chilling tendency, shrinkage
behaviour and mechanical properties of ductile iron
produced before and after the addition. The second group
of experiments run in the laboratory conditions consisted
of using different melting techniques such as ductile iron
additions to the base iron at the end of melting process or/
and holding the iron with undercooled tendency at a higher
temperature than normal (1565C or 2850 F). Addition of
ductile iron returns to already molten iron was performed
with the aim to improve the base iron nucleation potential
through dilution. The second technique used was intended to
dissipate the nuclei promoting undercooled microstructure.

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It was initiated based on the positive results obtained on the


grey iron in the first phase of the project. Details of the two
groups of experiments can be found in a CANMET report.3
This paper focuses on the most efficient additive(s) to
increase the nodule count in both base and ductile irons in
laboratory conditions. By increasing the number of graphite
nodules during solidification, the rate of release of latent heat
due to the graphite crystallization increases, and the end of
freezing temperature is raised above the cementite liquidus
line preventing carbide formation. Following the laboratory
experiments, tests were conducted under commercial foundry
operating conditions to verify the data obtained in laboratory.
Experimental Procedure
The laboratory experiments were performed in coreless
induction furnaces lined with alumina on a typical base
iron composition: 3.85% C; 1.85% Si; 0.3% Mn; max
0.03% P and 0.01% S and following a common melting
practice. Based on preliminary investigations that had
shown that if the graphitization ability of the charge
materials is poor, the nucleation potential of the iron
obtained after remelting will be certainly poor, all the
heats were produced with 50% highly carbidic ductile
iron returns in the charge. The nodularization treatment
was completed in a tundish ladle with 1.3% FeSi-6%
Mg- 1%Re along with 0.3% foundry grade ferrosilicon as
inoculant.

Results and Discussion


Microstructure
Data from image analysis of the as-polished microstructures
indicated that the best effect on the number of graphite
separations and acceptable nodule morphology was obtained
in ductile iron after the addition of 0.3% SiC: the nodule
number meeting the image analysis criteria increased by
64%. After the addition of SiC diluted with FeSi75% (0.2%,
Mixture Y) the nodule count increased by 15%. 0.05% SiCa
and/or 0.1% crystalline graphite produced an increase in
nodule count by only 3.5% and 2.5% respectively. Mixture
X and/or FeS had a negative effect on the nodule count: the
nodule count decreased 19%. Variation of total graphite
separations and the density of the nodule meeting the criteria
established for image analysis are shown in Fig. 1.

Density, Nodule no./mm2

The metallurgical additives selected to be investigated as


potential sources of active elements providing suitable sites for
graphite nodule nucleation are the following: SiC, a mixture
of 50% SiC with 50% FeSi5%Mg (Mixture X), a mixture of
50% SiC and 50% foundry grade FeSi75% (Mixture Y), SiCa,

FeS and crystalline graphite. The metallurgical additives were


introduced into the molten iron in the furnace, wrapped in a mild
steel foil to facilitate sinking and to avoid oxidation or sticking
to the crucible walls. Their effect was monitored by comparison
with the ductile iron initial state on test samples taken before and
after addition for each experiment. The following test samples
were poured: chill wedges to determine chilling tendency, 25
mm diameter rods for microstructural examination and tensile
test bars. Pin samples were taken from base iron before and after
addition to determine variations in total oxygen and nitrogen
contents. Thermal analysis data was recorded to determine
undercooling and recalescence. Changes in the microstructure,
chilling tendency and mechanical properties of ductile iron
were investigated and the data evaluated. Tensile testing was
performed only on samples poured from ductile iron with an
increased nodule number and improved chilling tendency after
the addition was made.

Figure 1. Variation of total graphite content and nodule number.

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Before

After

0.3% SiC

0.2% Mixture X

0.2% Mixture Y
Figure 2. Nodule size distribution in ductile iron produced before and after the additions. (Figure contd on next page.)

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Before

After

0.05%SiCa

0.01%FeS

0.1% crystalline graphite


Figure 2. Nodule size distribution in ductile iron produced before and after the additions. (Contd from previous page.)

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After

Before

0.3% SiC

0.2% Mixture X

0.2% Mixture Y
Figure 3. Effect of various additions on ductile iron chilling tendency. (figure
continued on next page.)

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Before

After

0.05%SiCa

0.01%FeS

0.1% crystalline graphite


Figure 3. Effect of various additions on ductile iron chilling tendency.
(Continued from previous page.)

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SiC had a positive effect, as well, on the nodule characteristics:


0.3%SiC addition produced an increase of the Nodularity
count by 21%, Sphericity by 2.4% and Roundness by 2.4%.
The addition of 0.1% crystalline graphite had an insignificant
effect on nodularity and roundness, while Mixture X and FeS
additions affected adversely the nodule characteristics.
The frequencies of nodule size variation in each test sample,
poured before and after addition, as shown in Fig. 2. SiC
alone or mixed with FeSi75% produced also an improvement
of the nodule size distribution: the small (4-16 m) nodule
number increased and the large (16-64 m) nodule number
decreased (Fig. 2). Previous published research has shown
that the skewed distribution of the nodule size and the
increase of the number of the small and late nucleated
nodules affect positively the ductile iron properties and that
the large nodule numbers are detrimental to ductile iron
properties including shrinkage tendency.1,2
Examination of the etched microstructures indicates that
the average amount of ferrite and pearlite in the reference
ductile iron samples were about 32 % and 58 % respectively.
Addition of SiC mixed with Fesi75% had the most beneficial
effect on ferrite formation followed by the crystalline
graphite, which increased by 20% and 14% respectively.
SiC produced only 3% increase in ferrite content.

Thermal analysis data indicate that the initial state of iron


varied from heat to heat presenting different degrees of
undercooling. Undercooling of the base iron(s) varied from
21.84C (71.31F) to 9.11C (48.4F) and ductile iron
between 27.47C (81.45F) and 18.66C (65.59F) . Thus,
pouring reference samples for each heat was mandatory for
making a correct assessment on the effect of investigated
additions on the nucleation potential of the iron.
Variations of undercooling and recalesence of the base
and ductile irons determined on the samples taken before
and after each addition are represented graphically in
Figs. 4 and 5. Undercooling is defined as the difference
between the gray iron eutectic temperature (TEgray =
1153 +6.7*Si) and the actual low eutectic temperature
(TElow). It characterizes the iron tendency for undercooled
microstructure. A high undercooling also means a longer
time before freezing starts and in consequence an increased
risk for macro shrinkage and outer sunk. Data show that
SiC alone or mixed with FeSi75% has a beneficial effect
on undercooling: the decrease in the base iron was about
22%; in ductile iron the decrease was 7.4% and 0.6%
respectively for the two additions. FeS produces as well
a decrease of undercooling even though the nodule count
decreased. All other metallurgical additives were followed
by an increase of undercooling in both base and ductile
irons by comparison with the initial state of iron.

Undercooling, C

Analysis of the chill wedges taken from ductile iron (Fig. 3)


indicates less carbides in the samples after addition of SiC,
Mixture Y and crystalline graphite respectively. The chill

wedge samples taken after SiCa, FeS and Mixture X indicate


an increase in carbide content.

Figure 4. Undercooling variation in the base and ductile irons.

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Data from thermal analysis proved as well the correlation


between the undercooling tendency of the base iron and
that of ductile iron: an increase in undercooling of the base
iron produces an increase of undercooling in ductile iron
and vice-versa.

The gas test results show that the addition of SiC, mixture
Y, FeS and crystalline graphite produced an increase
of total oxygen content in the base iron between 4 and
9 ppm. Data analysis shows that there is a correlation
between the increase of total oxygen content and the
increase of nodule number in ductile iron, with the
exception of the heat with FeS addition where the nodule
number decreased. Thus, the increase in total oxygen
content in the base iron is not a sufficient condition to
generate an increase of nodule number in ductile iron.
All the additions made produced an increase in the
nitrogen content in base iron between 1 and 3 ppm, but
these variations could not be related with the changes in
nodule number of ductile iron.

Recalescence, C

Data on recalescence indicate that only SiC, alone or mixed


with FeSi75%, and FeS had a beneficial effect leading to
a decrease in recalesence in both base and ductile irons.
A high recalescence in ductile iron is often an indication
of low nodule count4 but the correlation did not always
work.5 When comparing the effect of metallurgical
additions on recalesence versus nodule count, data show
that when the recalesence decreases, the nodule count
increases and vice versa. Exception is FeS addition
showing that while recalesence decreased in ductile iron
from 4.57C to 1.62C (40.23F to 34.92F), the nodule
count decreased from 164 nodules /mm2 to 132 nodules/
mm2. Lower nodule count after FeS addition could be
caused by a lower Mg available for nodularization after
the addition of 0.017%FeS since the quantity of FeSi Mg
was deliberately the same in all other experiments.

Data analysis show a good correlation between the trend of


undercooling measured by thermal analysis and the variation
of the amount of carbides in the ductile iron wedges with
the exception of the samples taken after the crystalline
graphite. The amount of carbides in the wedges poured after
the graphite addition is smaller while thermal analysis data
indicate an increase in undercooling.

Figure 5. Recalescence variation in the base and ductile irons.

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Mechanical Properties

Technology Demonstration

Based on microstructural and thermal analysis results, the


samples produced with SiC alone and mixed with FeSi75%
and 0.1% cristalline graphite were selected for tensile
tests. Four specimens were tested for each condition. The
results indicate that the addition of SiC caused an increase
of elongation from 16 to 23%, tensile strength from 511 to
522 MPa and yield strength from 333 to 346 MPa. Also, the
tensile properties of the samples produced with SiC were
more consistent, with a relatively lower standard deviation
by comparison with the reference samples. The addition
of SiC diluted with FeSi75 resulted in very little increases
in elongation and tensile strength. The graphite addition
resulted in increased tensile properties as well: % elongation
from 19 to 21%, ultimate tensile strength from 545 to 552
MPa, and yield strength from 348 to 357 MPa.

Based on the laboratory results, ductile iron tests were


organized in an industry. Unfortunately for this study the
foundry did not have iron with increased undercooling
tendency. The experiments were run in an induction furnace
on iron with the typical chemical composition: 3.67% C,
2.43% Si, 0.27% Mn, 0.026% P, 0.046% Mg. After melting
the charge materials, the reference samples were poured.
Then 0.3%SiC was added to the furnace and the second set
of test samples was taken. Test samples were poured from
both base and final irons before and after addition.

In conclusion, the results of the investigation under laboratory


conditions show that the addition of 0.3%SiC to the base iron
was the most efficient metallurgical additive for increasing
the nucleation potential (nodule count) in ductile iron,
improving undercooling tendency and upgrading tensile
properties, primarily % elongation.

The as-polished microstructures of ductile iron samples


poured for reference had an average of 156 nodules /mm2,
32% ferrite and only 0.14% carbides. After 0.3%SiC addition
the nodule count increased to 241 nodules /mm2. The nodule
roundness improved from 0.708 to 0.717 and sphericity from
0.880 to 0.891. Typical microstructures of the samples poured
before and after SiC addition are shown in Figures 6 and 7
respectively. The etched microstructures indicate a much
higher increase in ferrite content than in the samples produced
in laboratory: the ferrite content increased from 32% to 51%.
The carbide content already very low, decreased to 0.10%.

Before: 156 nodules/mm2

Before: 37% ferrite, 53.4% pearlite

Figure 6. Typical microstructures in as-polished and etched samples taken before the SiC addition.

After: 241 nodules/mm2

After: 51.1% ferrite, 39.4%pearlite

Figure 7. Typical microstructures in as polished and etched samples taken after the SiC addition.

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Before

After

Figure 8. Nodule size distribution before and after 0.3%SiC addition.

Before

Ductile iron

Base iron

After

Base iron

Ductile iron

Figure 9. Chilling tendency in the wedges poured from the


base and final iron, before and after 0.3% SiC addition.

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SiC proved to be beneficial with respect to the frequencies of


nodule size as shown in Fig. 8 the large nodule number, with
the size between 32-64 m, decreased from 19% to 11%.
Chilling tendency was quantified visually by comparative
examination on both base and ductile irons on the chill wedges
poured before and after the SiC additions. The ductile iron
samples were polished and etched to reveal the white zone
formed at the tip of the chill test samples. The chill wedges
indicate that 0.3% SiC addition improved chilling tendency
of both base and ductile irons (see Fig. 9).
Unfortunately the data for thermal analysis were collected
with different equipment and the data did not correlate with
the trend shown by the microstructural examination.
The tensile properties determined on test specimens
machined from 30 mm diameter rods indicate an increase
in % elongation from 8.7% to 10.1% and a decrease of UTS
from 528 MPa to 505MPa. This reflects on the increase of
ferrite content following the SiC addition.
The results obtained under industrial conditions confirm the
beneficial effect of 0.3% SiC addition on nucleation potential
of ductile iron producing an increase of nodule count and a
decrease of chilling tendency of ductile iron.
Conclusions
1. SiC is the most efficient addition to obtain an
increase of the iron nucleation potential and at the
same time to obtain a decrease of the undercooling
tendency of the iron.
2. The beneficial effect of the SiC addition on the
microstructure is reflected in tensile test results:
the ultimate tensile strength increased by about
2%, the yield strength by 4% and the elongation
by 44%. In addition, the standard deviation for the
tensile properties diminished.
3. The effect of SiC diluted with FeSi75% (Mixture
Y) was beneficial to the iron quality to a smaller
extent in comparison with SiC alone.
4. The effect of crystalline graphite addition to the
iron with initially increased undercooling tendency
was negative.

8. There is a correlation between the undercooling


tendency of both the base and ductile irons: an
increase in undercooling in base iron led to an
increase of undercooling in ductile iron.
9. Data also confirmed the correlation between
recalesence and nodule count: an increase in
recalescence indicates an increase in nodule count.
10. The chill wedge tests and the cell number of the
base iron could not provide sufficient information
to predict the undercooling tendency of the ductile
iron.
11. Data on the oxygen content compared with the
nodule number variation indicate that an increase
in total oxygen level in the iron is not a sufficient
condition to determine an increase in nodule
number.
Acknowledgement
The authors would like to express their gratitude to AFS for
funding this work, Brillion Foundry for supplying ductile
iron with undercooled microstructure, Rio Tinto Iron and
Titanium for machining the tensile bars, R. Eagleson for
mechanical testing and all the members of the Experimental
Casting Laboratory for melting and casting.
REFERENCES
1. Popescu, M., Thompson, J., and Zavadil, R.,
Restoring Techniques for Monday Morning Iron,
Phase I, Report
MTL 2001-4(TR-R).
2. Popescu, M., Zavadil, R, Thompson, J. P., Sahoo,
M. and Gassere, P., Studies to Improve Nucleation
Potential of Ductile Iron When Using Carbidic Ductile
Iron Returns, AFS Transactions, vol. 115, pp 591-608
(2007).
3. Popescu, M., Zavadil, R, Thompson, J. P., and Sahoo,
M, Restoring Techniques for Monday Morning Iron,
Phase II, Report MTL 2005-14(TR-R).
4. ATAS Verifier Users Guide-NOVACAST Foundry
Technology, 1994-1998.
5. D. Sparkman, The Thermal Analysis of Ductile Iron,
Copyright Foundry Information Systems, 1997.

5. The effect of SiC in combination with FeSiMg


(Mixture X) was negative with respect to total
acceptable nodules.
6. The effect of 0.05% SiCa addition was positive on
the nodule count but negative on undercooling and
recalescence.
7. The effect of FeS addition on undercooling was
positive in both base and ductile irons.

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