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Chunky graphite in ductile iron castings


R Kllbom *, K Hamberg ** and L-E Bjrkegren *.
* Swedish Foundry Association, Sweden, ** Chalmers University of
Technology, Sweden.

Abstract
Non-spherical graphite morphology is detrimental on the mechanical
properties of ductile iron castings. This includes the branched and
interconnected chunky graphite that occasionally occurs in the thermal
center of castings. In this work the graphite morphology in ferritic ductile
iron that contained chunky graphite was studied. Chunky graphite was
shown to be a progressively degenerated morphology of spherical
graphite. Attempts to investigate the presence and segregation patterns of
elements that might play a role in the still concealed formation and growth
mechanism of chunky graphite were made. No macro segregation was
detected. The possible role of micro segregation of trace elements was
discussed but could not be determined. The graphite nucleation potential
seemed to be low in the chunky graphite areas due to the lack of available
oxygen and/or sulphur.
Key words ductile iron,
segregation, nucleation

graphite

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morphology,

chunky

graphite,

Introduction
Spherical graphite morphology is an important factor to attain high quality
ductile iron castings. Every other type of morphology is detrimental on the
mechanical properties. This includes the branched and interconnected
chunky graphite that occasionally occurs in the thermal center of ductile
iron castings. The presence of chunky graphite decreases the ultimate
tensile strength (Rm) and especially the fracture elongation (A5). The
possible decrease in a ferritic ductile iron has been shown to reach 25%
and 50% respectively depending on the amount of chunky graphite [1].
However, the hardness (HBW) and the yield strength (Rp02) are hardly
affected at all by chunky graphite. Regarding the dynamic properties of
almost 100% chunky graphite containing material the crack propagation
rate is not significantly affected but the fracture toughness of the material
will be lower [2].
The risk of chunky graphite formation is increasing with long solidification
time. Consequently, the amount of chunky graphite tends to increase with
increased wall thicknesses [1]. The call for further research work to
determine the cause and growth mechanism of chunky graphite is
escalating with increased used of heavy section ductile iron castings in
demanding applications within the heavy automotive and the windmill
industries among others.
According to Gagn and Argo chunky graphite shows a spiral crystal
growth pattern caused by carbon supersaturation and constitutional
supercooling as the driving forces [3]. Fast diffusion rate due to the lack of,
or partially disrupted, austenite shell around the graphite nodule has also
been discussed as one possible cause for chunky graphite formation [3].
According to Itofuji et al the chunky graphite forms as a result of the lack of
magnesium gas bubbles in the melt and, further on, the growing graphite
is in contact with residual liquid iron through thin liquid channels in the
austenite [4]. The liquid channels are formed when segregated elements
lower the solidus temperature. Liu et al regards the chunky graphite to be
a deteriorated form of nodular graphite [5]. It has in fact been observed
that the transition between the graphite structures type A flake, type B
flake, type D undercooled flake, coral, compacted, chunky and spherical
graphite is continuous and not intermittent [6]. The different morphologies
were stated, by Liu et al to occur as a result of change in solidification rate
and as a function of alloy addition or segregation [6].
In this work the graphite morphology in ferritic ductile iron that contains
chunky graphite has been studied and attempts have been made to
investigate the presence and segregation patterns of elements that might
play a role of the concealed formation mechanism of chunky graphite.
Experimental
High silicon alloyed ductile iron were prepared in a 250 kg induction
furnace. The charge material consisted of pig iron 41 %, returns 17 % and

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steel scrap 42 %. Furan bonded moulds were used to cast a pattern


consisting of five 200 mm x 200 mm blocks with thicknesses ranging from
10 to 200 mm. The temperature change of the melts was logged during
solidification using thermocouples placed in the center of each block. The
solidification time ranged from 90 seconds to 90 minutes for each block
respectively. Besides the blocks a component cast in the same silicon
alloyed ductile iron has been investigated. The component is a front axle
housing aimed for a dumper. Specimens were cut out from an area with a
hot spot with fairly long solidification time (approx. 30 min).
Tensile test bars were machined, perpendicular to gravitational direction,
from the center of the blocks and from the components. The graphite
morphology was studied in the fracture surfaces of the bars using SEM.
The microstructure was studied in different positions within the test bars
using conventional optical microscope. The deep etched technique used
consisted of 40 minutes etching in a mixture of HCl and HNO3 (3:1)
followed by a cleaning step in Vogels etchant and thereafter well rinsed in
ethanol. Some specimens were color etched in boiling sodium hydroxide
(10g) + picric acid (10g) + potassium pyrosulfite (10g).
Using GD-OES (Glow Discharge Optical Emission Spectroscopy)
investigation of macro segregation was made, comparing nodular and
chunky graphite areas within the same 200 mm cubic block.
Measurements were made in up to six positions located 10, 20, 30, 45, 60
and 90 mm from the cast surface. The analyzed positions are indicated in
Figure 1.
SEM with EDS as well as EPMA were used as analyzing tools in orders to
investigate micro segregation tendencies.
Results
Graphite morphology
Chunky graphite is mainly located in the thermal center. Nevertheless, the
chunky graphite zone can represent a reasonably large volume of the
casting. This is exemplified by Figure 1 where the presence of chunky
graphite appears as a shaded area in a sawed cross section. Some areas
within the dark zone consist of nodules but the main graphite morphology
is chunky, Figure 2. From Figure 1 it appears as the transition from
nodular to chunky graphite growth happens very sudden in an interrupted
manner. However, optical microscopy and SEM studies of the graphite
morphology put forward a gradual change.
The graphite morphology in the vicinity of chunky graphite areas in this
200 mm cubic casting is classified to be a mixture of form IV to VI
according to the standard EN ISO 945:1994. Large irregular graphite
lumps, which cannot be classified by the standard, as well as very small
islands of chunky graphite, are also found in those areas, Figure 3.

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The examined fracture surfaces of the tensile test bars are located within
the chunky graphite zone shown in Figure 1. SEM investigations of
graphite in the fracture surfaces indicate gradual degeneration from
spherical to chunky morphology. Figure 4 shows well-shaped nodules.
Approaching chunky graphite areas different graphite morphologies as in
Figure 5 and 6 can be observed. These observations, that chunky graphite
is a progressively degenerated morphology of nodules, are in line with the
theory of Liu et al [5]. The degenerated graphite shape in Figure 7 and the
pyramidal growth of chunky graphite branches in Figure 8 confirm the
observations of Liu et al [5].
All specimens from the front axle housing showed somewhat different
graphite morphology compared to the 200 mm thick block. In most
locations normal spherical graphite morphology emerged. Roughly 15%
degenerated chunky graphite appeared at the most in the hot spots.
Figure 9 shows a typical area, here the cell boarders appear in a brown to
white color. The blue etching parts in the microstructure contain
degenerated graphite and do appear before the brownish cell boarders.
Here two variants of degenerated graphite can be seen. One type of
graphite that appears as normal chunky graphite (see Figure 10 in deep
etched condition) and one more like a stringer of graphite (Figure 11).
These graphite stringers lie between the secondary dendrite arms. The
classical chunky graphite seems to be placed in the center of the dendrite
arms. In all cases the degenerated graphite can co-exist with spherical
graphite.
Segregation of elements
Bulk analyzes did not show any significant difference in chemical
composition between the different positions indicated in Figure 1. Some
variations could be seen in Si content, for example, between different
positions but no coupling to chunky graphite could be confirmed. Macro
segregation between the nodular areas outside the chunky graphite zone
as well as inside the zone was hence not detected, Table 1.
Attempts to investigate micro segregation tendencies of low content
elements such as Ce, Ca and S in the blocks by using EPMA turned out to
be unsuccessful since the concentrations were below the detection limit of
the instrument. This was a fact close to spherical graphite as well as
nearby chunky graphite. The average Si content was somewhat higher
near the chunky graphite compared to that near a nodule. Nevertheless,
the difference was not greater than the Si fluctuation between two
nodules.
Closer investigations of the graphite in the front axle housing show some
differences. The stringer like graphite had in most cases been nucleated
on oxides. Spot analysis of the oxide particles revealed normal oxides
containing Si and or Mg. The melts that produced the components had a

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rather high amount of residual magnesium content, 0.060-0.065 (%), this


might explain the amount of particles with high magnesium content. The
stringer graphite is not considered to be a chunky graphite variant.
In order to find evidence of micro segregation further investigations were
made with SEM EDS. Mapping, spot and line analysis were tried without
much success. The only evidence of segregation was found in the Si and
Mn content between graphite particles. No evidence of tramp elements
like the elements mentioned in the literature [1], were found. A possible
reason is a relatively small concentration of the mentioned elements and
an insensitive analyzing method. The method gave the response from a
too great material volume that disturbed the analysis.
Further, spot analyses in two types of areas, chunky and nodular, as
depicted in Figure 12 were carried out. The focus was on systematic
analysis of particles found during the EDS-mapping. A majority of the
small particles (<10 m) were found in the eutectic cell borders between
nodular and chunky graphite areas, typical location is shown in Figure 12.
However, particles were also found in the nodular area as well as in the
chunky area close to the borderline. The amount of particles was greater
in the cell border areas than in the chunky graphite areas. The chemical
composition of the particles was not the same in all areas. In the cell
borders and in areas with nodular graphite, the particles contained Mg, O
and Si (see Figure 13). Some particles contained Ti and C. Frequently the
particles in those areas also contained P and S. On the other hand, in the
chunky graphite areas the number of particles was small. Most of the
particles in those areas contained Mg and S but no oxygen. Trace of Al
and Ca were found as well.
Discussion
During solidification the condition in the melt is gradually, but rapidly,
changing to be more favorable for the chunky graphite growth manner.
Different authors have debated the change in melt condition that promotes
the chunky graphite growth. Several theories indicate, as mentioned in the
introduction, that the cause of chunky graphite is related to the chemical
composition of the melt. Heavy section castings with long solidification
times are more prone to develop chunky graphite. The graphite
precipitation and growth start out to be nodular and then changes towards
chunky. Consequently, it can be assumed that variations in concentration
due to segregation of certain elements might be a possible reason for the
transition of graphite morphology growth. The elements Ca, Si, Al, Ni, Ce
and other RE are said to promote chunky graphite, especially in absence
of the elements Sn, As, Bi, B, Sb and Pb [1].
However, in this work no macro segregation of elements was found.
Further, the role of micro segregation could not be determined since the
chemical concentrations were too low to be detected by conventional
analyzing methods.

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Nevertheless, the evaluation of the results of this work renders a


hypothesis that the collaboration between Mg, S and O is important for the
chunky graphite formation. Skaland has depicted the nucleation sites for
spherical graphite [7]. The substrate contains a MgS core circumscribed
by a shell of magnesium silicate, normally MgOSiO2. Skaland denote this
substrate type A. Active elements introduced to the melt by inoculation,
such as Ca, Ba, Sr and Al, will react with the magnesium silicate and form
a hexagonal substrate that is a favorable site for graphite precipitation. If
oxygen (or sulphur) is not present the needed hexagonal nucleus will not
form.
The irregular graphite often found in microstructures of castings that
contain chunky graphite (as Figure 3) indicates in fact low oxygen content
in the melt. The Mg-treatment was experimentally well performed and the
Mg content is high enough to produce nodular graphite. No vermicular
graphite can be found at all. Therefore the irregular graphite consequently
indicates insufficient inoculation. However, since the inoculation procedure
was good it can be assumed that the inoculation has not worked properly
due to low oxygen content.
In this work, an excess of Mg/O/Si containing particles was found in the
areas containing graphite nodules as well as in the borderline between
nodular and chunky areas. Therefore, one can assume that the nucleation
requirements for spheroidal graphite can be fulfilled in those areas. A
consequence, however, is that the areas containing nodules consume
most of the oxygen. A strong indication for this is that only MgS particles
are found in the chunky graphite areas demonstrating that the oxygen
level has been too low to form the hexagonal structure that are needed to
favor spherical graphite growth. The graphite nucleation is disturbed and
chunky graphite will form between the nodular areas.
Besides Mg, elements as Ca, Al, Si, Ce consume oxygen by forming
stable oxides. This further strengthens the hypothesis, that low available
oxygen content might be a reason for chunky graphite formation, since
these elements also are said to promote chunky graphite.
Conclusions
1. The branched chunky graphite is a progressively degenerated
morphology of spherical graphite.
2. Unstable or changing melt condition during the solidification leads to
chunky graphite formation, a change that is still not fully defined.
3. In chunky graphite areas MgS particles were found while the amount of
magnesium oxides was limited compared to the areas that contained
spherical graphite.
4. The lack of available oxygen (or possibly sulphur) to form nuclei for
spherical graphite precipitation might be a reason for chunky graphite
formation.

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5. Macro segregation was not found to be a reason for chunky graphite


formation. The role of micro segregation could not be determined.
References
1.
Kllbom R, Hamberg K, Bjrkegren L-E, Chunky graphite
formation and influence on mechanical properties in ductile cast
iron, Gjutdesign 2005 Final seminar, Espoo, Finland, 13-14 June,
2005, VTT Technical Research Centre of Finland, Finland, 2005.
2.
Bjrkblad A, Conventional vs closure free crack growth in nodular
iron, Gjutdesign 2005 Final seminar, Espoo, Finland, 13-14 June,
2005, VTT Technical Research Centre of Finland, Finland, 2005.
3.
Gagn M and Argo D, Heavy Section Ductile Iron Castings Part I
and Part II, International Conference on Advanced Casting
Technology, Kalamazoo, Michigan, USA 12-14 November 1986,
pp 231-256, ASM International.
4.
Itofuji H and Uchikawa H, Formation Mechanism of Chunky
Graphite in Heavy-section Ductile Cast Irons, AFS Transactions
90-42, 1990, pp 429-448.
5.
Liu P C, Li C L, Wu D H and Loper, Jr, SEM Study of Chunky
Graphite in Heavy Section Ductile Iron, AFS Transactions 83-51,
1983, pp 119-126.
6.
Liu P C, Loper Jr C R, Kimura T and Park H K, Observations on
the graphite morphology in cast iron, AFS Transactions 80-41,
1980, pp 97-118.
7.
Skaland T, A model for the graphite formation in ductile cast iron,
NTH Trondheim, 1992, ISBN 82-7119-384-8.
Acknowledgements
The Nordic Innovation Centre and VINNOVA partly financially supported
this work. The authors thank Volvo Construction Equipment for supplying
the front axle housings (prototypes).
Tables
Table 1 GD-OES analyzes of chemical composition inside and outside the
chunky graphite zone. The location of analyzed positions is shown in
Figure 1.
Pos
Si
Mn
P
S
Cu
Al
B
Sn
Ca
Ce
Sb

1
3.05
0.19
0.071
0.016
0.020
0.012
0.0013
0.024
0.0001
<0.001
0.005

2
3.38
0.16
0.059
0.013
0.018
0.012
0.0006
0.025
0.0002
<0.001
0.003

MELT 1
3
4
3.27
3.31
0.17
0.18
0.055
0.047
0.014
0.016
0.019
0.021
0.013
0.013
0.0009 0.0011
0.024
0.024
0.0001 0.0002
<0.001 <0.001
0.003
0.004

5
3.26
0.19
0.055
0.016
0.021
0.013
0.0011
0.020
0.0002
<0.001
0.003

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6
3.29
0.18
0.067
0.015
0.021
0.013
0.0011
0.022
0.0002
<0.001
0.003

2
3.36
0.18
0.046
0.017
0.018
0.014
0.0010
0.025
0.0001
<0.001
0.003

MELT 2
4
6
3.30
3.55
0.21
0.19
0.072
0.062
0.018
0.014
0.019
0.019
0.014
0.015
0.0016 0.0013
0.020
0.020
0.0001 0.0001
<0.001 <0.001
0.006
0.006

Figures

1 2 3 4 5 6

Figure 1 Chunky graphite


zone located in the thermal
center (200 mm cube).
Numbers denote positions of
analyzes, see Table 1.

Figure 2 Graphite morphology in


the thermal center of a 200 mm
cube (105 X)

Figure 3 Mixture of graphite shapes


just outside the chunky zone (45 X)

Figure 4 Well-shaped nodules


(750 X)

Figure 5 Approaching chunky


graphite areas the graphite gradually
changes its morphology (350 X)

Figure 6 Transition state in the


border of a chunky graphite cell
(1000 X)

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Figure 7 Degenerated graphite


(2000 X)

Figure 8 Pyramidal growth of


chunky graphite branches
(deep etched 1500 X)

Figure 9 Color etched microstructure


containing chunky graphite.

Figure 10 Deep etched graphite


that looks like classical chunky
graphite.

Figure 11 Stringer graphite that is not


considered to be chunky graphite.

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Figure 12 Particles were detected in the borderline between chunky and


nodular graphite areas as well as in each area respectively.

Figure 13 Particles in the borderline and in the nodular areas (see Figure
12) were composed of these elements. The peak to the left is not valid for
the analyze.

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