See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/289972447

Dross in Ductile Iron: Source, formation and explanation

Article · January 2008

CITATIONS READS
7 918

3 authors:

M. Gagné Marie-Pierre Paquin

32 PUBLICATIONS   277 CITATIONS   
Rio Tinto Alcan
1 PUBLICATION   7 CITATIONS   
SEE PROFILE
SEE PROFILE

Pierre Cabanne
Rio Tinto
5 PUBLICATIONS   26 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Production of pig iron by utilizing biomass as a reducing agent View project

All content following this page was uploaded by Pierre Cabanne on 03 May 2018.

The user has requested enhancement of the downloaded file.

 Dross in Ductile Iron: Source, Formation and Explanation
by
Martin Gagné, Marie-Pierre Paquin and Pierre-Marie Cabanne
Rio Tinto Iron and Titanium

ABSTRACT
The manufacture of Ductile Iron (DI) castings has to obey basic rules.
Although the production of sound castings exhibiting the required
mechanical properties is easily achieved, the casting user also asks for a
casting skin finish without apparent defects. Defects such as dross and
slag affect the surface appearance of the parts but, more importantly,
affect the fatigue endurance by acting as initiation sites for the failure. As a
result, producing castings free of dross becomes an important challenge
for foundries producing either thin wall or heavy section castings. This
paper presents a study on the formation of dross at different temperatures
and chemical compositions. The experience of the Rio Tinto R & D group,
through many investigations carried out on DI samples, has lead the
researchers to investigate dross formation with a simulation software. It
was observed that the formation of dross is directly connected to the level
of oxygen while the iron temperature modifies the dross composition. The
dross built-up is marginally affected by sulphur and the influence of
magnesium and silicon was confirmed.
Key words: Ductile iron, dross, slag, heavy casting, simulation
Introduction
Ductile Iron, over a period of sixty years, has become a major engineering
material with a production, in 2008, exceeding 20 million tons. Unless grey
iron, whose production tends to stagnate, Ductile Iron enjoys growth
exceeding 3% per year, confirming the interest for this material which is
challenged by the perception that Ductile Iron may exhibit defects inherent
to its production.
When the production process of Ductile Iron is compared to that of grey
iron, additional processing steps are required but the need of the
spheroïdization treatment usually carried out with Mg alloys remains the
most striking difference between grey and Ductile Irons. While essential to
ensure the crystallization of spheroïdal graphite particles, the use of
magnesium has a few drawbacks, one of them being the formation of
magnesium silicate inclusions. The objectives of this article are to review
the nature of such inclusions oftentimes called drosses, and their effect on
mechanical properties and, using thermodynamic modeling, to identify
process conditions that favour their formation.
What is “Dross”?
Different types of non-metallic inclusions can be found in Ductile Iron
castings and may be divided into three major categories. The most easily
recognizable ones are sand particles. As seen in Figure 1a, these are
angular particles analyzed as containing 100% silica (see Table 1). The

1
second type of non-metallic inclusions is slag. As sand inclusions, these
particles are exogenous inclusions, i.e. they form prior to pouring the metal
into the mould and are entrained in the metal during pouring. Examples
are presented in Figures 1a and 1b. These inclusions, identified as slag
defects, are oxides that form by the reaction of the treatment and
inoculation alloys or of residuals present in the iron; Table 1 lists typical
compositions of such inclusions. As seen in this table, inclusion C-1 is
composed of MgO and SiO2 and has a filamentary shape, while others
have a more complex composition and a more massive appearance. The
elongated, filamentary type inclusions are “dross” particles.
Figure 2 presents examples of dross defects found in various castings;
Table 2 presents the composition of the castings. It is seen in Figure 2 and
Table 2 that the formation of dross, which has been reported to be
favoured by high magnesium and silicon contents, is detected in castings
with magnesium and silicon contents as low as 0,033% and 2,19%,
respectively (Figure 2b). The range of carbon content covered (3,28–4,12)
also indicates no relationship between dross and carbon content.
However, as shown in Figure 2c, dross may be associated with graphite
floatation, since both graphite and dross have lower densities than liquid
iron. A common feature of dross stringers is that they are coated with a
quasi-continuous graphite film. This coating becomes thicker as the
carbon content increases as seen in Figure 2c.
The dross particles of Figure 2 and others were analyzed by Energy
Dispersive X-Ray (EDX) analysis. The results are listed in Table 3. As
noticed in Table 2, the castings investigated were low in sulphur content
(0,008% max.). As seen in Figure 3, which is a typical EDX spectrum of
dross shown in Figure 2a (0,006%S), no sulphur peak was detected,
identifying the dross stringers as oxides. Note that sulphur is occasionally
found in dross, but its presence is not required for dross formation.
Although sulphur compounds are not always detected in dross, flake
graphite is often observed in their vicinity. Figure 4 shows an area from the
casting of Figure 2c, which contains only 0,008%S. It is seen that the
dross found in this area contains iron oxide, implying that all magnesium
was oxidized (according to the Ellingham diagram) and no magnesium
was available to ensure graphite spheroidization. It may also be the result
of the transformation of MgS to MgO; then, sulphur enrichment of the
surrounding iron causes the formation of flake graphite.
When examining the compositions listed in Table 3, it is clear that dross is
the result of the reaction of oxidizable elements with oxygen, the most
reactive elements being in a decreasing order magnesium, aluminium,
calcium, silicon, manganese and iron. However, due to higher silicon
content in the castings (2 to 3%), silicon oxidation is favored in most
cases. The MgO content varies from 14 to 48%, although the Mg content
of the casting remains in a relatively tight bracket, 0,030 - 0,050%,
indicating that factors other than % Mg control dross formation.

2
Effect on Mechanical Properties
Figure 5 shows the results of a test program carried out at a foundry to
study the variability of the tensile properties on castings from the same
ladle. It is seen that the castings contained between 8% to about 20%
pearlite and that the relationship between the elongation and pearlite
content was linear. However, a few results show significant deviation. The
examination of the fracture of such bars indicated that the reduction of
elongation was caused by the presence of large inclusions, Figure 6a,
identified as a planar inclusion of graphite and dross.
The effect of dross on mechanical properties has mainly been investigated
with regards to fatigue properties, since it tends to float on the upper
surface of a casting and/or under a core surface. It then becomes a
surface defect acting as a stress raiser that facilitates fatigue crack
initiation. Although the nature of the dross particles found in the castings
tested (exogenous or endogenous) is often not clear in literature, its effect
on the fatigue characteristics of Ductile Iron was significant. Reduction in
fatigue endurance from 20 to 50% was reported in literature[1,2,3].
Modeling of Dross Formation
The influence of foundry parameters on dross formation has been
investigated by many researchers[4,5,6,7]. The most influential factors were
identified as pouring temperature, atmosphere (oxygen), Mg content,
carbon equivalent,… However, because of the difficulty to isolate all
process parameters during the production of castings, it is not clear what
parameter has the greatest influence on dross formation, and conflictual
results are often reported. In order to understand the influence of various
parameters on its formation, dross formation was modeled using a
thermodynamic simulation program known as “Fact Sage”. (Facility for the
Analysis of Chemical Thermodynamics)[9]. This software calculates the
thermodynamic equilibria using thermodynamic data bases for pure
elements and compounds.
Table 4 lists the range of chemical compositions tested. Note that initial
calculations were carried with the assumption that sulphur content was
negligible to assess the effect of oxygen content without interference from
sulphur. Although not specifically related in this paper to discrete
turbulence index or exposure to oxygen, it is assumed that increasing the
oxygen level in the iron is related to increased turbulence.
Figure 7 shows the simulation results, i.e. the amount of dross forms as a
function of temperature for different oxygen contents. The major points to
conclude from these five figures are the following:
i) At low oxygen content (< 100 ppm), inclusions formed are SiO2 and
MgO (isolated or combined) usually found as discrete small particles.
ii) Magnesium silicates, which tend to be “planar” inclusions, appear at
about 300 ppm oxygen. Under these conditions, SiO2 does not form. At
about 500 ppm oxygen, MgO disappears and only magnesium silicates
are found.

3
iii) As the oxygen content further increases, drosses become a mixture of
MgSiO3 and Mg 2SiO4. At high oxygen content (1000 ppm), SiO2 is
formed, because Mg is not available to form magnesium silicates.
iv) The effect of temperature on dross formation is seen only at high
oxygen contents; the amount of dross decreases for temperatures
higher than about 1400oC.
v) The amount of drosses continually increases with the exposure to
oxygen; at 100 ppm O2, it is about 0,04% and 0,12 – 0,2% at 1000.
The effect of casting composition, i.e. % S, % Mg and % Si, on dross
formation was also simulated. The results are shown in Figure 8, for
simulations run at 1300 and 1500oC. The following conclusions can be
drawn:
i) Magnesium sulphides form in the drosses if oxygen content is less than
about 300–400 ppm whatever the composition and temperature. That
explains the absence of sulphur in most dross particles as well as the
formation of flake graphite around the particles. MgS will be found in
dross when the exposure to oxygen is limited (less turbulence) or if
rapid solidification occurs.
ii) At low temperature (1300oC), the total amount of dross formed is
similar for the two compositions tested (Figures 8a and 8c). However,
as the magnesium content increases from 0,04 to 0,06%, the nature of
the dross changes from MgO + Mg2SiO4 + MgSiO3 + SiO2 to mainly
Mg2SiO 4 + MgO.
iii) At high temperature (1500oC), higher Mg and Si contents result in a
significant increase in the amount of dross formed i.e. 0,18% vs 0,12%
but the composition of the dross remains similar (Figures 8b and 8d).
iv) At high temperature (1500oC), the maximum amount of dross formed is
achieved at 600 ppm O2 for a casting containing 2% Si and 0,04% Mg
and at 800 ppm for a casting containing 2,5% Si and 0,06% Mg.
v) The decrease of dross formation and the changes of composition as
the iron temperature increases are confirmed.
From this analysis, it appears that the major factor controlling the
formation of planar magnesium silicate inclusions (dross) is the amount of
oxygen in contact with liquid iron. The critical concentration of oxygen
needed for the formation of such inclusions is about 300 – 400 ppm for all
conditions tested. Such a concentration is reached when the surface of
liquid iron is exposed to an oxygen rich atmosphere; these conditions exist
when pouring liquid iron in the mould or if the iron is exposed to oxygen
due to turbulence or poor gating system design in the mould.
An increased iron temperature was found to reduce dross formation, but
mainly with high exposure to oxygen. Therefore, sacrificing the benefits of
low pouring temperature when producing heavy section castings to reduce
dross formation would be efficient but limited in the case of high exposure

4
to oxygen. The effect of increasing Mg and Si contents on dross formation
has been seen only at high temperature.
Conclusions
From this study on the formation of planar magnesium silicate inclusions
(dross), it can be concluded:
1. Dross, as defined as planar magnesium silicate inclusions, can be
found in Ductile Iron castings of chemical composition typical of thin
and/or heavy section parts.
2. The presence of planar dross inclusions was confirmed as being
detrimental to mechanical properties.
3. The composition of planar dross inclusions varies, with the major
constituents being MgSiO3 and Mg2SiO4. The variability of the
composition is strongly related to the exposure to oxygen.
4. Sulphur compounds may occasionally be present in planar dross
inclusions but are not an essential component of the inclusions.
5. The major factors controlling planar dross formation are, in the
decreasing order, the concentration of oxygen to which the liquid iron
is exposed, the temperature of the iron and the Mg and Si contents.
6. According to the simulation results, reducing the iron temperature
decreases dross formation only in presence of very high oxygen
concentration.
References
1. P.R. Kan et al, Flow of Ductile Iron Through Ceramic Filters and
the Effects on the Dross and Fatigue Properties, AFS
Transactions, vol. 95, 1987, pp 105-116.
2. F.S. Starley and P.E. Irving, Int. J. Fatigue, July 1982, pp 129-
136.
3. P. Refstie, AFS Casting Congress, St-Louis, April 2005.
4. R.W. Heine and C.R. Loper, Dross Formation in the Processing
of Cast Iron, AFS Transactions, vol. 74, 1966, pp 274-280.
5. P.K. Trojan et al, An Intensive Investigation of Dross in Nodular
Cast Iron, AFS Transactions, vol. 76, 1968, pp 323-333.
6. M.C. Latona et al, Factors Influencing Dross Formation in
Ductile Iron Castings, AFS Transactions, vol. 92, 1984, pp 881-
906.
7. D.R. Askeland et al, Investigating of Mechanisms of Dross
Formation in Ductile Iron, AFS Transactions, vol. 78, 1970, pp
125-132.
8. C. Bale et al, CALPHAD, 2002, pp 198-228.

5
Table 1 – Chemical Composition* of Inclusions Shown in Figure 1
Figure 1a 1b
Identification A B C-1 C-2 C-3
% SiO2 54 100 44 53 54
% MgO 17 - 52 16 -
% Al2O3 - - - 18 18
% CaO 18 - - - 10
% FeO - 15
* EDX analysis; does not sum to 100%.

Table 2 – Chemical Composition of Castings with Dross Defects

Element Figure 2a Figure 2b Figure 2c Figure 2d
C 3.55 3.62 4.12 3.28
S 0.006 0.003 0.008 0.003
Si 2.56 2.19 2.73 2.79
Mn 0.20 0.28 0.16 0.17
Mg 0.044 0.048 0.033 0.040
Ce 0.010 Not avail. 0.002 Not avail.
Al 0.018 0.016 0.014 0.028
Ca 0.001 0.002 0.005 0.005
CE 4.40 4.34 5.03 4.21

Table 3 – Typical Chemical Composition of Dross Particles from Figure 2

Analysis no. 1 2 3 4 5 6
MgO 25% 14 16 48 40 24
SiO2 56% 55 62 44 36 33
Al2O3 7% 5 8 5 6 1
CaO 0.5 - - - - -
MnO 5 23 11 - 3 8
FeO 4 3 2 2 16 31

Table 4 – Range of Chemical Composition Used in the Simulation Tests

Element Wt %
Si 2,0 – 2,5
Mg 0,004 – 0,006
O 0 – 900 ppm
S 0 – 0,020

6
 C1
1

C2
2

C3
3

Figure1a. Slag (A) and sand (B) Figure1b. Details of area (C) of
inclusions. Figure 1a.

a b

c d

Figures 2. Examples of dross defects in castings of various compositions

(see Table 2).

7
Figure 3 Typical EDX spectrum
of dross particles of figure 2a. No Figure 4 Area of flake graphite
sulphur was detected, as in most in a dross area of a low sulphur
particles analyzed casting (ref. Figure 2c)

22

20

18
Elongation (%)

16

14

12

10

8
7 9 11 13 15 17 19 21 23
Pe rlite Conte nt (%)

Figure 5. Elongation vs Pearlite content for a series of castings Poured

from the same ladle.

a b
Figure 6. Fracture surface of Sample with a low elongation showing the
presence of a planar inclusion identified as graphite covering
dross oxides.

8
 Dross formation (g) at different temperature (°C) Dross formation (g) at different temperature (°C)
100 ppmO - 0.04%Mg - 2% Si 300 ppmO - 0.04% Mg - 2% Si
0.050 0.080

0.070
0.040
Mg2SiO4
SiO2 0.060

0.030 0.050
dross ( g )

d ross ( g )
0.040

0.020
0.030 MgO
MgO
0.020
0.010

0.010

0.000 0.000
1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500
T (C) T (C)

7a 7b

Dross formation (g) at different temperature (°C) Dross formation (g) at different temperature (°C)
500 ppm O - 0.04% Mg - 2% Si 700 ppmO - 0.04% Mg - 2% Si
0.120 0.160

0.140
0.100
0.120
0.080
0.100
dro ss ( g )

Mg2SiO4
d ro ss ( g )

0.060 0.080

0.060
0.040
0.040
Mg2SiO4
0.020 MgO
0.020
MgSiO3
0.000 0.000
1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500 1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500
T(C) T (C)

7c 7d
Dross formation (g) at different temperature (°C)
1000 ppmO - 0.04% Mg - 2%Si
0.250

0.200
dross ( g )

0.150

0.100
MgSiO3
0.050
Mg2SiO4
SiO2
0.000
1300 1320 1340 1360 1380 1400 1420 1440 1460 1480 1500
T (C)

7e

Figure 7 Effect of iron temperature and oxygen content on dross formed

in an iron with very low sulphur content.

9
 0,01%S-2,0%Si -0,04%Mg -1300 °C 0,01%S-2,0%Si -0,04%Mg-1500°C
0.240 0.240
0.220 0.220
0.200 0.200
0.180 0.180
0.160 0.160
dross ( g )

dross ( g )
0.140 0.140
0.120 0.120
0.100 0.100
0.080
Mg2SiO4 MgSiO3 0.080
0.060 0.060 Mg2SiO4
0.040 0.040 S
0.020 MgS MgO Mg MgO
SiO2 0.020
0.000 0.000
0.001 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 0.001 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1
%O %O

a b

0,02%S-2,5%Si -0,06%Mg-1300°C 0,02%S-2,5%Si -0,06%Mg-1500°C

0.240 0.240
0.220 0.220
0.200 0.200
0.180 0.180
0.160 0.160
dross ( g )

dross ( g )

0.140 0.140
0.120 0.120
0.100 Mg2SiO4 0.100
Mg2SiO4
0.080 0.080
0.060 0.060
0.040 Mg
S
0.040 MgS MgO
0.020 MgO MgSiO3 0.020
0.000 0.000
0.001 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 0.001 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1
%O %O

c d

Figure 8 Effect of oxygen concentration, iron temperature and

composition on the formation of dross.

10

View publication stats