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Effect of Sulfur on the Formation of the Graphite Degradation in Ductile Iron

Article  in  Materials Science Forum · March 2017

DOI: 10.4028/www.scientific.net/MSF.895.89

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Materials Science Forum Submitted: 2016-12-20
ISSN: 1662-9752, Vol. 895, pp 89-93 Accepted: 2017-01-09
doi:10.4028/www.scientific.net/MSF.895.89 Online: 2017-03-30
© 2017 Trans Tech Publications, Switzerland

Effect of Sulfur on the Formation of the Graphite Degradation

in Ductile Iron
Sarum Boonmeea and Nupol Mai-Ngam
School of Metallurgical Engineering, Suranaree University of Technology, Thailand
a
sarum@sut.ac.th

Keywords: Casting skin; Graphite degradation; Ductile iron; Magnesium depletion; Skin thickness

Abstract. The objective of this study is to evaluate the effect of sulfur in core sand on the formation
of the graphite degradation in ductile iron. The graphite degradation is caused by the depletion of
Mg in liquid iron resulting in low nodularity zone underneath the casting surface. The content of
sulfur in molding materials has been known as an important factor of the occurrence of the graphite
degradation. It was found that the greater content of sulfur in the core sand promoted the formation
of the graphite degradation. The graphite degradation with the thickness ranged from 113 to 1116
m was observed for the sulfur content from 0.24 to 1.68 wt%S.

Introduction
The negative effect of casting skin on the mechanical properties has been demonstrated by several
investigators [1-5]. The casting skin features can be categorized into surface and subsurface
features. The surface feature is simply the surface roughness. The subsurface features are i) graphite
depletion ii) graphite degradation iii) ferritic rim iv) pearlitic rim.
The casting skin feature that creates the most deleterious effect is the graphite degradation
(shown in Figure 1). The graphite degradation refers to the transition of the graphite morphologies
from nodular to compacted and to lamellar. The mechanism of this transition was explained by the
depletion of Mg in the liquid iron [6]. The depletion of Mg can be a result from oxidation and/or
desulfurization. Since these phenomena generally occur at the mold/metal interface; hence, the
graphite degradation usually presents at the casting skin as a layer underneath the casting surface.

Figure 1. Graphite degradation in ductile iron.

As most iron castings are used without machining on all surfaces, the actual strength can be
significantly lower than the machined counterpart (i.e. standardized samples). The reduction of
tensile and fatigue strength approximately 10% and 40% respectively were reported [3-5].
As desulfurization is one of the formation mechanism of the graphite degradation; therefore, the
origin of sulfur in the system should be investigated. Typically, some sulfur from the raw materials
may be presented in the liquid iron. However, this does not cause the graphite degradation as the
addition of Mg eliminates effect of sulfur in the melt. Another source of sulfur is the catalyst used
(Para Toluene Sulfonic Acid, PTSA) in molding process. In addition, sulfur in molding sand can be
accumulated through the sand reclamation in which contributes to the Mg depletion [7,8].

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90 Material Engineering and Smart Materials

Other affecting parameters on the formation of the graphite degradation are pouring temperature,
level of Mg in iron melt and casting thickness. This study aims to assess the effect of the sulfur
level on the formation of the graphite degradation in ductile iron.

Experimental Procedure
In this study, a test casting was designed to accommodate the evaluation of several sulfur levels in
the same casting. As seen in Figure 2, one mold accommodated four sodium silicate cores. Other
design considerations are as follow,
 The design must provide the quiescent filling to avoid the erosion on cores by liquid iron
 The cooling rate must be comparable with industrial castings. The value of 0.5 C per
minute was used as the design target.
 The temperature distribution in the cores must be comparable or with subtle difference.
 The casting must be free of shrinkage porosity.
 To avoid the mottled structure, the characteristic cooling rate of the casting was kept less
than ~10oC/s.
To achieve the above criteria, a simulation software package were used to evaluate the filling
and solidification behaviour of the test casting.
The cores contained various sulfur levels by adding FeS powder (ground to -250 mesh size) e.g.
0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0 and 3.5 wt%FeS (48%S – balanced Fe) which translate to 0, 0.24, 0.48,
0.72, 0.96, 1.20, 1.44 and 1.68 wt%S respectively. The addition processes started by mixing of the
virgin foundry sand and FeS powder. Once thorough mixed, the sodium silicate resin was added
and continually mixed until homogeneous. The mix was then packed in the core box and exposed to
carbon dioxide (also known as cold box process). The cope and drag were made by typical green
sand molding.

Figure 2. Test casting used in present study.

40 kg of iron was produced using an induction furnace. The Mg treatment was done by the
sandwich method using the FeSiMg as the nodularizer. The tapping temperature was approximately
1450 C. All conditions were poured with same melt for the consistency.
The microstructure examination and thickness measurement were done with an image analyzer
software. Figure 3a shows the measurement method for the thickness of the graphite degradation.
The method can be described as follows; establish a line for the casting surface; draw series of lines
perpendicularly to the established casting surface line; the distance from the casting surface line to
the rim of the graphite degradation layer represents the thickness. The process was repeated for 100
times for one sample. The average thickness was then calculated from,
n

Y i
(1)
Thickness  i

n
where Yi is the distance obtained from measurement i; n is number of measurement (n = 100).
Figure 3b demonstrates the measurement of the nodularity of graphite. As seen, the graphite
particles were detected and categorized into groups based on their roundness. The details of
measurement can be found in the ASTM A274 standard. The steps were repeated to evaluate the
nodularity as a function of distance from casting surface.
 Materials Science Forum Vol. 895 91

(a) (b)
Figure 3. Measurement method for (a) thickness of graphite degradation (b) nodularity.

Results and discussion

Table 1 shows the chemical composition of ductile iron produced in this study. As seen, the carbon
equivalent was 4.14 indicating the hypoeutectic composition. The Mg/S ratio was relatively high
(Mg/S = 5.42). This was intentional to minimize the graphite degradation layer for the control
condition. It should be noted that this level of Mg/S ratio is also similar to the industrial ductile iron
production.
Table 1. Chemical composition (by weight percent).
C Si Mn P S Mg
3.25 2.67 0.0347 0.0366 0.0104 0.0564
Figure 4 shows the representative microstructures next to the cores at various sulfur levels. It is
seen that the graphite degradation layer was not observed for the control condition. This was due to
the high Mg/S ratio which minimized the Mg depletion at the mold/metal interface. At higher sulfur
levels, the thickness of the graphite degradation layers increased. This confirms the Mg depletion
due to the desulfurization theory. The graphite degradation layer as thick as 1000 – 1400 m was
readily recorded at 1.68 wt%S. In addition, the variation of the data increased as the thickness
increased. This is due to the curviness of the graphite degradation rim which is typically seen.
Some graphite flotation was also observed. This was expected because the locations were at the
bottom of the cores and no inoculation was done to the melt.

(a) 0 wt%S (b) 0.24 wt%S

(c) 0.96 wt%S (d) 1.20 wt%S

(e) 1.44 wt%S (f) 1.68 wt%S

Figure 4. Representative microstructures next to cores with various sulfur levels.
92 Material Engineering and Smart Materials

Figure 5 shows the nodularity as a function of distance from the casting surface (with 1.50%S in
core sand). It is seen that the nodularity was low at the graphite degradation layer. Proceeding
inward, the nodularity increased with the distance and stabilized at approximately 80%. It should be
noted that there is an abrupt change in nodularity at the interface between the graphite degradation
layer and the bulk microstructure. This observation was consistent in all conditions which implied
that the nodularity can be used to measure the thickness of the graphite degradation layer. It should
be noted that there was no clear high nodularity zone adjacent to the graphite degradation layer
which was observed readily in compacted graphite iron [3]. Presumably, the high nodularity zone
could have been obscured by the higher bulk nodularity in ductile iron.

Figure 5. Nodularity as a function of distance from the surface.

Figure 6 shows the relationship between the thickness of the graphite degradation layer and the
levels of sulfur in the core sand. As expected, the thickness increased with the increasing sulfur
levels. This can be explained by diffusion of sulfur. Sulfur from the cores diffused into the liquid
iron causing the Mg depletion zone through the desulfurization. The higher level of sulfur provided
the greater composition gradient in which increased the diffusion rate; hence the thicker graphite
degradation layer.
The Mg depletion due the oxidation could not be accounted as the main factor because of the
limitation of oxygen available (cores surrounded by liquid iron). Originally, the greater graphite
degradation at the core was expected due to longer solidification time than the external surface. The
longer solidification time should allow more Mg depletion; however, this was not the case due to
the limitation of oxygen.
An empirical equation was deduced from the results as,

Y = 337.23x2 – 0.8565x + 47.171 (2)

where Y is the thickness of the graphite degradation layer. The coefficient of determination (R2) was
0.9031 depicting the strong correlation. This equation is useful for predicting the thickness of the
graphite degradation layer. It should be noted that the equation could have been different for
difference Mg/S ratio.
 Materials Science Forum Vol. 895 93

Figure 6. Graphite degradation thickness as a function of sulfur levels in the core sand.

Conclusions
Present study aims to evaluate the effect of sulfur on the formation of the graphite degradation in
ductile iron. It can be concluded as follows,
 The thickness of the graphite degradation layer increased with the levels of sulfur presented
in the core sand. The graphite degradation with the thickness ranged from 113 to 1116 m
was observed for the sulfur content from 0.24 to 1.68 wt%S.
 The Mg depletion due the desulfurization was responsible for the effect. The phenomenon is
diffusion-controlled.
 The regression analysis provides an equation that can be used to predict the thickness of the
graphite degradation layer.

Acknowledgement
This work was made possible by the financial support from the National Research Council of
Thailand. The authors also would like to acknowledge ESI group for supporting the simulation
software and the Center of Scientific and Equipment, Suranaree University of Technology for
providing its facilities.
Mr. Mai-Ngam is thankful for the scholarship from the Research Institute, SUT.

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[3] G.M. Goodrich, R.W. Lobenhofer, Trans. AFS, 110, 1003 (2002)
[4] S. Boonmee, D.M. Stefanescu, Trans. AFS, 118, 217 (2010)
[5] S. Boonmee, M.K. Moran, D.M. Stefanescu, Trans. AFS, 119, 421 (2011)
[6] C. Labrecque, M. Gagne, P. Cabanne, C. Francois, C. Beret, F. Hoffmann, Int. J. Metalcasting,
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